CN1818012A - Nitride phosphor and production process thereof, and light emitting device - Google Patents

Nitride phosphor and production process thereof, and light emitting device Download PDF

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Publication number
CN1818012A
CN1818012A CNA200610005476XA CN200610005476A CN1818012A CN 1818012 A CN1818012 A CN 1818012A CN A200610005476X A CNA200610005476X A CN A200610005476XA CN 200610005476 A CN200610005476 A CN 200610005476A CN 1818012 A CN1818012 A CN 1818012A
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fluor
light
luminous
emitting device
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CN100509997C (en
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玉置宽人
龟岛正敏
高岛优
山田元量
内藤隆宏
阪井一彥
村崎嘉典
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Nichia Chemical Industries Ltd
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Nichia Chemical Industries Ltd
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Abstract

The invention provides a nitride phosphor, manufacture method thereof and a light emitting device, which provides a phosphor with more red component and higher luminous efficiency, luminance and durability, and manufacture method thereof. The phosphor is represented by the formula LXMYN((2/3)X+(4/3)Y):R or LXMYOzN((2/3)X+(4/3)Y-(2/3)z):R (L is selected from at least one of II-group elements comprising Mg, Ca, Sr, Ba and Zn, M is selected from at least one of IV-group elements comprising C, Si and Ge, wherein Si is a must element and R is selected from at least one of III-group elements comprising Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Lu, wherein Eu is a must rare-earth element.). The phosphor (substrate nitride phosphor) can absorb at least a portion of light of a first luminescent spectrum with a peak wavelength less than 500 nm and emit a light of a second luminescent spectrum with a wavelength between 520nm and 780 nm of one peak at the least and contains different elements.

Description

Nitride phosphor, its manufacture method and light-emitting device
The application's application number that to be the applicant propose on March 20th, 2003 be 03800454.2, denomination of invention is nitride phosphor, the date that dividing an application of the international application of its manufacture method and light-emitting device, this application enter country's stage is on December 17th, 2003.
Technical field
The illumination, indicating meter, use that the present invention relates to semiconductor light-emitting elements, luminescent lamp etc. with light-emitting device backlight etc., particularly relates to the nitride phosphor of use at light-emitting device at liquid crystal.
Background technology
The light-emitting device of use semiconductor light-emitting elements is small-sized and electrical efficiency is fabulous, and can carry out the luminous of distinct color, because light source is a semiconductor element, so have the advantage that needn't worry situations such as explosion.Even have initial stage drive characteristic excellence, vibration or conducting are disconnected the repeated extremely strong feature of lighting a lamp.
In addition, use the light-emitting device of semiconductor light-emitting elements, the part of the light by making semiconductor light-emitting elements via fluor is carried out wavelength conversion, and with the light of this wavelength conversion with the light that do not carry out wavelength conversion mixes and the measure of radiation, and exploitation has the light-emitting device of making the illuminant colour different with the light of luminous element.Particularly, carry out the luminous light-emitting device of white color system, be widely used in general illumination, indicating meter, liquid crystal with backlight etc. according to such formation.
In the light-emitting device of this white color system, adopt to use the blue based light-emitting device of InGaN material as luminous element, and as fluor use with (Y, Gd) 3(Al, Ga) 5O 12Composition formula and the YAG that represents is a fluor, the white color system illuminant colour obtains according to the colour mixture principle of light.Also promptly, self-emission device and the blueness that radiates system, in being incident upon luminescent coating after, after in layer, repeating absorption several times and disperseing, radiate toward the outside.On the other hand, worked as excitaton source by the blueness system that fluor absorbed, and emission xanchromatic fluorescence.Mix after this sodium yellow and the blue light, then the being seen white that is of people.
But above-mentioned white color system light-emitting device has on luminous that its red composition is less, and colour temperature is higher, and only to obtain the problem of the lower illumination light of red insufficient color developing.
Also promptly, in the past carry out the luminous light-emitting device of white color system owing to be difficult for obtaining long wavelength side luminous of visible region, so form the light-emitting device of blue a little white white color system.With respect to this, the illumination of the demonstration usefulness in shop or the illumination of medical on-the-spot usefulness etc., then the white color system light-emitting device that for the warm colour that has redness slightly is by strong request.In addition, as general illumination with also be the light-emitting device of approaching white color system to the comparatively soft bulb color of the eyes of human body by strong request.
Yet the fluor that red colour system in the past is luminous produces efficient and chemistry because of near ultraviolet to blue light excites, temperature is stable lower, so durability not insufficient is filled part, and can't reach practicability.In addition, in human eye,, promptly feel dim to the wavelength domain aspect of red composition.Therefore, in order to experience and brightness green, the blue region same degree, then red area must have higher brightness.
Following in like this situation, in the world disclose No. 01/40403 communique, announcement had the M that is compared to fluor in the past and increases red composition xSi yN z: (M is at least 1 of the alkaline-earth metal in the group of Ca, Sr, Ba, Zn at least for Eu.Z=2/3x+4/3y) nitride phosphor.
But, be disclosed in the international nitride phosphor that discloses No. 01/40403 communique, though for example obtain reddish white color system, also be required more to improve its brightness by making up with blue series LED.
In addition, the fluor that red colour system in the past is luminous produces efficient and durability not insufficient is filled part because of near ultraviolet blue system excites, and can't reach practicability.
In addition, when above-mentioned light-emitting device for example uses as routinely carrying out the luminous illumination light source of high light, because because of the heating of luminous element causes the launching efficiency of various fluor to reduce, so produce the problem that all light beams [Im] of light-emitting device reduce.And then will make up with a plurality of fluor that respectively reduce because of the heating launching efficiency in the time of forming light-emitting device for different ratios, because the difference of the luminous output of each fluor and the variation of surrounding temperature all produce change, observe light that light-emitting device penetrates and be phenomenon from the position color displacement of the chroma offset of expectation so produce a kind of meeting.
In addition, luminous element is because of importing the increase of electric current, and makes the peak wavelength of the luminescent spectrum of luminous element be passed to short wavelength side (for example with reference to Figure 56).Because of this peak wavelength is passed to short wavelength side, then the luminous intensity of excited fluorescent body promptly produces change according to luminous element.When particularly fluor being carried out the combination more than 2 kinds, the change of its luminous intensity produces bigger influence to color displacement.
Even like this small color displacement, and above-mentioned light-emitting device is for example when using as the light source of liquid crystal projector produces expansion is incident upon screen and the tone of the chromatic image shown causes the problem of very big influence.
And then when being that the YAG that exists in the scope of 500nm to 750nm is a fluor and to excite the peak wavelength of absorption spectrum be the red colour system fluor that exists in the scope of 350nm to 600nm with the wavelength of luminescent spectrum, also promptly since with respect to the reflection of light rate more than the wavelength 500nm for lower, so when forming with the red colour system fluor mixing that absorbs the light more than the 500nm and as luminescent coating, then the red colour system fluor promptly absorbs the luminous part that YAG is a fluor.Therefore, the YAG shown in Figure 80 is the peak wavelength of the luminescent spectrum of fluor, almost can't be discovered in the zone of wavelength 500nm to 550nm, and can't fully improve the color developing of the mixed light that selfluminous device exports.In addition, above-mentioned light-emitting device is for example as the luminous illumination light source that carries out high light of persistence and when using, because because of the heating of luminous element causes the launching efficiency of various fluor to reduce, so produce the problem that all light beams [Im] of light-emitting device reduce.And then will make up with a plurality of fluor that respectively reduce because of the heating launching efficiency in the time of forming light-emitting device for different ratios, because the difference of the luminous output of each fluor and the rising of surrounding temperature all change, so the colourity of the light that selfluminous device is emitted, the phenomenon of the color displacement that the position that generation is offset from the colourity of expecting is observed.
Even so small color displacement, above-mentioned light-emitting device produce expansion are incident upon screen and the tone of the chromatic image shown causes the problem of very big influence for example when using as the light source of liquid crystal projector.
Summary of the invention
Therefore, the present invention is in order to address the above problem, and its 1st purpose is containing more red composition providing, and luminous efficiency and brightness are higher, and also higher fluor and the manufacture method thereof of weather resistance.
In addition, the 2nd purpose of the present invention is providing the luminous of the white color system that can have red warm colour system, and can carry out the luminous light-emitting device of the higher light of color developing.
Even and then the 3rd purpose of the present invention is being compared to prior art and improves color developing providing, and surrounding temperature is when changing, also can be with the light-emitting device of the generation of the reduction that suppresses light beam [Im] or chroma offset.
For solving above-mentioned problem, relate to nitride phosphor of the present invention, with general formula L XM YN ((2/3) X+ (4/3) Y: R system or L XM YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): (L is selected from Mg in R system, Ca, Sr, Ba, more than at least a kind of II family element that Zn formed, M is selected from C, Si, the middle Si of Ge is necessary more than at least a kind of IV family element, R system is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, the middle Eu of Lu is necessary more than at least a kind of rare earth element) represented, has at least a portion that peak wavelength is the light of the 1st luminescent spectrum below the 500nm in absorption, and in the luminous nitride phosphor (substrate nitride phosphor) of the light that will have the 2nd luminescent spectrum that in the scope of 520～780nm, possesses the peak value more than at least 1, and then contain following element (below, be called different elements).
Also promptly, relate to the 1st nitride phosphor of the present invention, it is characterized in that: in above-mentioned substrate nitride phosphor, and then contain and be selected from the different elements more than at least a kind that Li, Na, K, R are the I family element formed of b, Cs.
This contains by Li, Na, K, R is the 1st nitride phosphor of the I family element formed of b, Cs, is compared to the nitride phosphor that does not contain I family element, has higher luminous efficiency.This is that the above-mentioned I of consideration family element is in synthetic, work as fusing assistant, after this, owing to the I family element that works as fusing assistant exists between fluorophor particle, or, be less cause and hinder the luminous situation of fluor because I family element forms the state that disperses in manufacturing process.In addition, by I family element is contained at nitride phosphor, can control the particle diameter of nitride phosphor.
In addition, relate to the 2nd nitride phosphor of the present invention, it is characterized in that: in above-mentioned substrate nitride phosphor, and then contain the V group element formed by V, Nb, Ta, be the element more than at least a kind in the group VIII element formed of u by VI family element that Cr, Mo, W formed, by VII family element that Re formed, by Fe, Co, IR system, Ni, Pd, Pt, R.
Be added with this type of the 2nd nitride phosphor of the present invention of V group element, VI family element, VII family element, group VIII element and the nitride phosphor that do not add this dvielement when comparing, then have the effect that can shorten twilight sunset.In addition, this type of element can carry out the adjustment of brightness.Herein, with different V group element, VI family element, VII family element, the group VIII elements of element that contains at the composition of above-mentioned nitride phosphor, it is to containing the weight at the element of the composition of above-mentioned nitride phosphor, serving as preferred below the 100ppm.This is to be the luminous colour killing element of the former nitride phosphor of obstruction because of V group element, VI family element, VII family element, group VIII element, so be preferred cause owing to significantly reduce the luminous efficiency removal.Its opposing face, Cr, Ni etc. are because have the effect that shortens twilight sunset, so also can contain 0.1ppm～number+ppm degree.
Also have, in the 1st nitride phosphor, and contain at the different element of the element of above-mentioned substrate nitride phosphor, it is for preferred below the 1000ppm to the weight that contains at the element of above-mentioned substrate nitride phosphor.If in this scope, promptly can carry out the adjustment of the characteristics of luminescence, and keep high brightness.The characteristics of luminescence in the specification sheets is meant with respect to the output characteristic of tone, brightness, twilight sunset, excitation intensity or luminous efficiency.
In addition, above-mentioned substrate nitride phosphor by Li, Na, K, R be the I family element formed of b, Cs, by V group element that V, Nb, Ta formed, by VI family element that Cr, Mo, W formed, by VII family element that Re formed, be selected from by Fe, Co, IR system, Ni, Pd, Pt, R be the element more than at least a kind in the group VIII element formed of u outside, or also can with this type of element all contain together with above-mentioned L, above-mentioned M, above-mentioned O, above-mentioned N, above-mentioned R be different elements (the 2nd different elements).
With general formula L XM YN ((2/3) X+ (4/3) Y: R or L XM YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): the nitride phosphor that R is represented, the rayed that will possess the 1st luminescent spectrum with peak wavelength during to blue region etc., then possess the nitride phosphor of the light of the 2nd luminescent spectrum with peak wavelength in ultraviolet in yellow to generations such as red area.By the 2nd different elements are contained at this nitride phosphor, promptly can not have and change tone and luminous intensity is changed.The nitride phosphor of the brightness with expectation promptly can be provided thus.In addition, can carry out the adjustment of brightness easily.
The different elements with the 2nd of above-mentioned different element get final product can contain in the raw material when making above-mentioned substrate nitride phosphor.Thus, no matter whether residual this type of different elements with the 2nd of different elements all can provide the nitride phosphor of the brightness with expectation on the fluor after the making.In addition, can carry out the adjustment of brightness easily.In addition, according to the raw material of regulating nitride phosphor of the present invention, for example the above-mentioned different elements in strontium nitride, CaCl2, silicon nitride, europium sesquioxide or the nitrogenize europium or the kind and the amount of the 2nd different elements can carry out the adjustment of brightness.In addition, contain the amount of the various elements in raw material, if can realize that its purpose is in the scope of the characteristics of luminescence time, can omit the refining step of raw material, and can reach the simplification of manufacturing process.Simultaneously also can be so that cheap goods to be provided.
For example, as the 2nd different elements, also can contain the I family element formed by Cu, Ag, Au, by iii group element that B, Al, Ga, In formed, by IV family element that Ti, ZR, Hf, Sn, Pb formed, by V group element that P, Sb, Bi formed, be selected from the element more than at least a kind in the VI family element of forming by S, and can carry out the adjustment of the brightness of substrate nitride phosphor by this type of element.In addition, Al, B, Ga, In etc. can carry out the adjustment of brightness and keep high brightness.
In addition, the amount of above-mentioned the 2nd different elements is serving as preferred below the 1000ppm.Thus, promptly can carry out the adjustment of the characteristics of luminescence easily.
When containing above-mentioned different elements or the 2nd different elements in the raw material when making above-mentioned substrate nitride phosphor, it serves as preferred containing in raw material with the scope below the 1000ppm.When reaching this scope, promptly can provide the nitride phosphor of brightness with expectation.In addition, can carry out the adjustment of brightness easily.
Firing process when making above-mentioned substrate nitride phosphor is to carry out in reducing atmosphere to preferably.By the operation of in reducing atmosphere, burning till, can promote dispersing of the unwanted element that comprised, and can reach the raising of luminosity.
The 1st manufacture method of nitride phosphor of the present invention is characterized in that containing:
The 1st operation, (the R cording has from Y its oxide compound that is with R, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, the middle Eu of Lu be in the necessary rare earth class more than at least a kind) and contain and be selected from by Li, Na, K, R is b, Cs, Cu, Ag, the I family element that Au formed, by B, Al, Ga, the iii group element that In formed, by Ti, ZR, Hf, Sn, the IV family element that Pb formed, by V, Nb, Ta, P, Sb, the V group element that Bi formed, by Cr, Mo, W, the VI family element that S formed, by the VII family element that Re formed, by Fe, Co, IR system, Ni, Pd, Pt, R is the compound wet mixing of the element more than at least a kind of the group VIII element formed of u;
The 2nd operation, its mixture that will obtain via the 1st operation burns till;
The 3rd operation, its will the nitride of the nitride of the obtained mixture of the 2nd operation, L (have be selected from the II family element of forming by Mg, Ca, Sr, Ba, Zn more than at least a kind) and M and the oxide compound of M (M have from the middle Si of C, Si, Ge be in the necessary IV family element more than at least a kind) any at least 1 mixing; And
The 4th operation, its mixture that will obtain via the 3rd operation in reducing atmosphere burns till.
Thus, promptly can provide brightness higher nitride phosphor.In addition, the element that can pass through to be added provides the nitride phosphor of the characteristics of luminescence with expectation.
At least one side of above-mentioned the 2nd operation and above-mentioned the 4th operation uses and contains by Li, Na, K, R is b, Cs, Cu, Ag, the I family element that Au formed, by B, Al, Ga, the iii group element that In formed, by Ti, ZR, Hf, Sn, the IV family element that Pb formed, by V, Nb, Ta, P, Sb, the V group element that Bi formed, by Cr, Mo, W, the VI family element that S formed, by the VII family element that Re formed, by Fe, Co, IR system, Ni, Pd, Pt, R is the crucible of the element more than at least a kind selected in the group VIII element formed of u and/or stove material and carry out firing process for preferred.Have crucible, the stove material of the element of the adjustment that can carry out the characteristics of luminescence by use, more can carry out the adjustment of the characteristics of luminescence easily.I family element uses as the calcining auxiliary agent when making crucible or stove material.In addition, I family element is easy to remain in the element in the raw material.Can use the monomer that adopts this type of I family element or the crucible or the stove material of compound, also can mix and burn till processing with the raw material of substrate nitride phosphor.Contain crucible, the stove material of I family element by use, promptly can carry out the adjustment of the characteristics of luminescence.Outside the I family element, it is preferred using crucible, the stove material of the element that contains B, Au, Ga, In etc., contains the measure of this dvielement and more can improve its brightness by use.
Relate to nitride phosphor of the present invention, though in its manufacturing process, add the element different with the composition of nitride phosphor, or contain the compound of this difference element, but in the operation of burning till, this difference element disperses, and in the composition of the nitride phosphor of final product, also have and only contain the situation of the element of addition amount still less more originally.Therefore, in the composition of the nitride phosphor of final product, just than the interpolation use level originally amount still less of this difference element for containing in composition.In addition, during the particle diameter of desire control nitride phosphor, can control by adding this difference element.
The 3rd nitride phosphor of the present invention, at least (R has the Y of being selected to have R, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, the middle Eu of Lu be in the necessary rare earth class more than at least a kind), and L (L has and is selected from by Mg, Ca, Sr, Ba, in the II family element that Zn formed more than at least a kind), and M (M has the C of being selected from, Si, the middle Si of Ge be in the necessary IV family element more than at least a kind), with the choosing by Li, Na, K, R is b, Cs, Cu, Ag, the I family element that Au formed, by B, Al, Ga, the iii group element that In formed, by Ti, ZR, Hf, Sn, the IV family element that Pb formed, by V, Nb, Ta, P, Sb, the V group element that Bi formed, by Cr, Mo, W, the VI family element that S formed, by the VII family element that Re formed, by Fe, Co, Ir, Ni, Pd, Pt, the element more than at least a kind in the group VIII element that Ru formed is characterized in that: this nitride phosphor is made according to above-mentioned the 1st manufacture method.
The 1st light-emitting device of the present invention comprises:
Luminous element, its light that will possess the 1st luminescent spectrum with the following peak wavelength of 500nm carries out luminous; And
Fluor, its absorption has at least a portion of the light of above-mentioned the 1st luminescent spectrum, and possesses the 2nd luminescent spectrum of the peak wavelength that has more than at least 1 in the wavelength region of 520～780nm; It is characterized in that:
Above-mentioned fluor has any of the 3rd nitride phosphor that the 1st nitride phosphor of the present invention, the 2nd nitride phosphor or the 1st manufacture method according to the present invention make.
In the 1st light-emitting device, the short wavelength side zone of the near ultraviolet visible light of above-mentioned nitride phosphor below 500nm is via from the light of the luminous element that possesses the 1st luminescent spectrum with peak wavelength and be excited.The nitride phosphor that is excited, to red area, the light that will possess the 2nd luminescent spectrum with peak wavelength carries out luminous in the yellow of 520nm～780nm.Thus, can provide and to carry out the luminous light-emitting device of bulb colour system.The bulb look is meant in the white according to JIS specification (JISZ 8110), is the scope at center with the point of 2700～2800K on the track of blackbody radiation, has yellow color to red colourity.Particularly, be meant pink, pink, (light) pink, (yellowing) white portion of (light) Huang Hong, (orange), have illuminant colour in the chromaticity coordinates kind of Fig. 8.
In addition, according to the 1st manufacture method of the present invention, promptly can make particle diameter be controlled in decide the fluor of scope.Therefore, in above-mentioned the 1st light-emitting device, by use particle diameter be controlled in decide the fluor of scope, can realize the few light-emitting device of phenomenon that uneven color claims.Can provide brightness higher light-emitting device more thus.In addition, in the prior art, do not change the tone of light-emitting device, and be difficult to make the characteristics of luminescence to change, but light-emitting device of the present invention, the characteristics of luminescence owing to nitride phosphor can be altered to expectation according to the effect of the element that is added changes the characteristics of luminescence so can not change the tone of light-emitting device.
Above-mentioned the 1st light-emitting device and then have the light of above-mentioned the 1st luminescent spectrum of absorption more than 1 and at least a portion of the light of above-mentioned the 2nd luminescent spectrum, can at blue region till green area, yellow area, the red area, make the light of the 3rd luminescent spectrum that possesses the peak wavelength that has more than 1 carry out luminous fluor for preferred.Passing through like this carries out the combination of luminous fluor and nitride phosphor of the present invention in various colourities uses, then can provide to have not only white, and the light-emitting device of the illuminant colour of soft etc. the expectation of color.In addition, even be white, also can (yellowing) be white to be tailored into, (general green) is white, (blueing) white etc.
The light of above-mentioned the 3rd luminescent spectrum is carried out luminous fluor, the yttrium that is activated with cerium at least. the yttrium that aluminum oxide is fluor, be activated with cerium at least. gadolinium. aluminum oxide is fluor and the yttrium that is activated with cerium at least. gallium. aluminum oxide is that any at least of fluor serves as preferred more than 1.The light-emitting device of the illuminant colour with expectation can be provided thus.For example, the yttrium that uses nitride phosphor of the present invention and be activated with cerium. when aluminum oxide is fluor etc., can produce the white color system of the various colourities of excited by visible light according to the combination of this type of fluor.
Above-mentioned the 1st light-emitting device, according to from the part of the light of above-mentioned luminous element, from the part of the light of fluor and from the colour mixture of any light more than 2 of the part of the light of fluor, and make the light of various whites (the strong white of blueing or general red strong white etc.) can carry out luminous with above-mentioned the 3rd luminescent spectrum with above-mentioned the 2nd luminescent spectrum.This light-emitting device can provide the white color system light-emitting device of expectation by adjusting the use level of various fluor.For example, according to luminous element with blue light, and nitride phosphor is excited, and carry out yellow ruddiness luminous, in addition, carry out luminous fluor by light and be excited and carry out the luminous of sodium yellow above-mentioned the 3rd luminescent spectrum, and between extruding nitride phosphor and fluor and the blueness of coming system, the yellow ruddiness of nitride phosphor and the sodium yellow of fluor, then because of the principle of the colour mixture of light, and in people's eye, be considered as white.
In the present invention, above-mentioned L, M, N, O, R and different elements or the 2nd different elements, though usually add with oxide compound or water oxide compound, but the present invention is not limited to this, also can be metal, nitride, imide, acid amides or other inorganic salts, in addition, also can be for containing state in advance at other raw material.In the composition of above-mentioned nitride phosphor, the situation that contains aerobic is arranged also.Oxygen can be considered to be imported by the various oxide compounds that constitute raw material, or oxygen is sneaked into the situation of burning till in the processing.This oxygen promotes Eu diffusion, the effect that particle diameter is grown up, crystallinity improves.Also promptly, will use a compound at raw material to change over metal, nitride, oxide compound and also can be to obtain identical effect, it be bigger situation that the effect when using oxide compound is also arranged.Nitride phosphor has the crystalline texture of oblique crystal, iris etc.
In addition, relate to the of the present invention the 1st and the 2nd nitride phosphor, can at random adjust persistence characteristic.Can continue to show and the display unit that repeats that as the indicating meter of PDP, CrT or LED etc. its persistence characteristic forms problem.The white color system light-emitting device that semiconductor light-emitting elements and fluor made up uses as the backlight of outdoor indicating meter or LED.Such purposes is required to possess short persistence.Therefore, by B, Mg, Cr, Ni, Al etc. being contained measure, can suppress twilight sunset at the substrate nitride phosphor.
Above-mentioned nitride phosphor, its median size are that 2.5～15 μ m are for preferred.Particularly 3～8 μ m more preferably.When particle diameter is big, then has luminosity and improve, and can improve the advantage that light is obtained efficient etc.
As above-mentioned, the of the present invention the 1st and the 2nd nitride phosphor can carry out the adjustment of the characteristics of luminescence of tone, brightness, twilight sunset etc. easily.In addition, can control the characteristics of luminescence, cheapness, and provide nitride phosphor according to easy manufacturing process.The 1st light-emitting device of the present invention can provide the luminous efficiency white color system light-emitting device that fabulous reddish warm colour is.In addition, can be provided in the yellow that makes up with blue based light-emitting device etc. and use nitride phosphor with luminescent spectrum to red area.Therefore, the present invention's meaning of technical elements of having the manufacture method that nitride phosphor, nitride phosphor can be provided and using the light-emitting device of this fluor.
As above-mentioned, according to the present invention, promptly can be provided at the yellow that makes up with blue based light-emitting device etc. and use to red area, have the nitride phosphor of luminescent spectrum.Use nitride phosphor that the luminous efficiency white color system light-emitting device that fabulous reddish warm colour is can be provided.
In addition, the present invention can with the element of the brightness of the fluor that can descend and can to improve the element of brightness of fluor specific.Thus, promptly can reach crucible, firing furnace preferably the changing of material, and can provide brightness higher fluor.
In addition, can provide with particle diameter be controlled at decide the nitride phosphor of scope.
And then has a meaning of the very important techniques aspect of the nitride phosphor that the raising that reaches weather resistance can be provided.
For solving above-mentioned problem, the 4th nitride phosphor of the present invention, contain: according to being selected from by Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, the rare earth element more than at least a kind in the group that Lu formed and being selected from of being activated by Be, Mg, Ca, Sr, Ba, the II family element more than at least a kind in the group that Zn formed, and be selected from by C, Si, Ge, Sn, Ti, ZR, the IV family element more than at least a kind in the group that Hf formed, and N, it is characterized in that: it is below the above 10000ppm of 1ppm that this nitride phosphor contains B.Thus, can reach the raising of the characteristics of luminescence of luminosity, quantum yield etc.The reason that can obtain effect like this is considered to according to the interpolation boron, and the diffusion that produces activating agent, and the growth of promotion particle.In addition, boron enters in the crystal lattice of nitride phosphor, eliminates the distortion of this lattice, and directly helps lighting means, and reach the improvement of the characteristics of luminescence of luminosity, quantum yield etc.
The representative of above-mentioned the 4th nitride phosphor, the Ca that is activated by Eu and any at least 1 nitride phosphor that element, Si and N formed of Sr.In the nitride phosphor of its typical example, the part of Eu can be replaced according to the rare earth element more than a kind that is selected from the group of being made up of Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Lu at least.The part of the element of at least any one party of Ca and Sr can be replaced according to the II family element more than a kind that is selected from the group of being made up of Be, Mg, Ba, Zn at least.The part of Si can be replaced according to the IV family element more than a kind that is selected from the group of being made up of C, Ge, Sn, Ti, ZR, Hf at least.
In the composition of the 4th nitride phosphor of the present invention, also can contain O.Thus, owing to can use the oxygen containing raw material of bag, can be easy to make.
The 5th nitride phosphor of the present invention is with general formula L XM YN ((2/3) X+ (4/3) Y): R system or L XM YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): (L is selected from least a above II family element in the group of being made up of Be, Mg, Ca, Sr, Ba, Zn in R system.M is selected from the IV family element more than at least a kind in the group of being made up of C, Si, Ge, Sn, Ti, ZR, Hf.R system is selected from the rare earth element more than at least a kind in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Lu.X, Y, Z0.5≤X≤3,1.5≤Y≤8,0＜Z≤3) expression, it is characterized in that: this nitride phosphor, contain below the above 10000ppm of B1ppm.Thus, can reach the raising of the luminous efficiency of luminosity, quantum yield etc.
The 6th nitride phosphor of the present invention, it is a part that absorbs light with the 1st luminescent spectrum, and in the zone different with above-mentioned the 1st luminescent spectrum, the light that will have the 2nd luminescent spectrum carries out luminous nitride phosphor, it is characterized in that:, contain under can be and the B that adds addition control state freely to the raw material of above-mentioned nitride phosphor.Thus, promptly can carry out the adjusting of the characteristics of luminescence of luminosity, quantum yield, twilight sunset etc.When not adding boron, the characteristics of luminescence of its luminosity, quantum yield etc. is fixing, but by adding boron, then reaches the raising of luminosity, and can shorten twilight sunset.Since the characteristics of luminescence in response to illumination with, show the purposes use etc., and the characteristic difference that it is required is so can obtain to change with same hue the characteristics of luminescence.
Also have, the 1st luminescent spectrum is excited via external device (ED).
The above-mentioned the 5th and the crystalline texture of the 6th nitride phosphor, serve as preferred with oblique crystal or orthorhombic nitride phosphor.Above-mentioned nitride phosphor can possess fabulous luminous efficiency by having oblique crystal or orthorhombic crystalline texture.
As above-mentioned rare earth element, be that the necessary element more than at least a kind serves as preferred with Eu.By Eu is used at active imparting agent, can provide the orange extremely red luminous fluor that carries out.By a part of replacing Eu with other rare earth element, can provide have different tones, the nitride phosphor of different persistence characteristic.
The the above-mentioned the 5th and the 6th nitride phosphor, and its to be selected from by Li, Na, K, R be that at least a above I family element in the group formed of b, Cs comprises below the 0.1 above 500ppm for preferably.Thus, promptly can reach the raising of the characteristics of luminescence of luminosity, quantum yield etc.This be because above-mentioned I family element in synthetic, work as fusing assistant, after this, owing to the I family element that works as fusing assistant exist in fluorophor particle between, or, be less so be regarded as hindering the luminous situation of fluor because I family element disperses in manufacturing process.In addition, by I family element is contained at nitride phosphor, can control the particle diameter of nitride phosphor.
The the above-mentioned the 5th and the 6th nitride phosphor, and then it is by I family element that Cu, Ag, Au formed, by iii group element that Al, Ga, In formed, by IV family element that Ti, ZR, Hf, Sn, Pb formed, contained below the 0.1 above 500ppm for preferred by the V group element that P, Sb, Bi formed, the element more than a kind in the VI family element that S formed at least.Thus, can carry out the adjustment of the brightness of nitride phosphor.
The the above-mentioned the 5th and the 6th nitride phosphor, so any element of its Ni, Cr to contain 1 above 500ppm following for preferred.Thus, promptly can shorten the twilight sunset of nitride phosphor.Outside Ni, the Cr, Mg, Al also have identical effect.By controlling the addition of this type of Mg, Al, Ni, Cr, can control twilight sunset.
The the above-mentioned the 5th and the 6th nitride phosphor, its median size is serving as preferred below the 15 μ m more than 2.Particularly, median size to be to serve as preferred below the 12 μ m more than 3, more preferably median size more than 5 below the 10 μ m then.Decide in the scope by particle diameter is controlled at, the situation that promptly can provide uneven color to claim is few light-emitting device.Can provide brightness higher light-emitting device thus.The median size of nitride phosphor is bigger, and then luminosity is higher, but when it becomes 15 μ m more than and use during at light-emitting device, then is difficult for applying, and is not easy to processing.On the other hand, the median size of nitride phosphor is littler, and then when being coated in the face of light-emitting device, though can carry out luminously equably, its luminosity is lower, or when coating and when manufacturing, has not tractable problem.Therefore, the median size with above-mentioned scope serves as preferred.
The 2nd light-emitting device of the present invention is to have:
Excitation light source, it goes out from the light radiation of near ultraviolet with the short wavelength zone of visible light; And
Fluor, it absorbs at least a portion from the light of this excitation light source, and will than the light of excitation light source more the light radiation in long wavelength zone go out; Light-emitting device, it is characterized in that:
Above-mentioned fluor has the of the present invention the 5th and the 6th nitride phosphor at least.The fabulous light-emitting device of luminous efficiency of luminosity, quantum yield etc. can be provided thus.In this 2nd light-emitting device, excitation light source goes out from the light radiation of near ultraviolet with the short wavelength zone of visible light.The part irradiation fluor of the light that is radiated out.Fluor absorbs the part of irradiated light and carries out wavelength conversion.The light of this wavelength conversion has the light of the wavelength of long wavelength side from the light of this excitation light source.Thus, promptly can provide the light-emitting device that can show from the illuminant colour of the illuminant colour of excitation light source and different colourities.During concrete illustration, use near the blueness the 460nm carried out luminous excitation light source, and with this rayed at nitride phosphor of the present invention.This nitride phosphor has near the extremely red illuminant colour of yellow 580nm～650nm.But,, promptly can provide the light-emitting device of illuminant colour with expectation by nitride phosphor is carried out various changes.
Above-mentioned fluor, so have the fluor of fluor, the green emitting of blue-light-emitting, Yellow luminous fluor more than at least 1 for preferred.Not only white according to carrying out the measure that the combination of luminous fluor and nitride phosphor of the present invention is used to various colourities, and promptly can provide having, and the light-emitting device of the illuminant colour of the expectation of soft middle shade etc.In addition, even be white, also can (yellowing) be white to be tailored into, (general green) is white and (blueing) white etc.And then have white by using any at least fluor more than a kind, promptly can providing with the fluor of the fluor of the excitation light source of near ultraviolet light radiation and nitride phosphor, blue-light-emitting, green emitting and Yellow luminous fluor, the light-emitting device of the expectation illuminant colour of soft middle shade etc.
Above-mentioned excitation light source is preferred with the semiconductor light-emitting elements.By using semiconductor light-emitting elements, can provide the light-emitting device of the feature that produces semiconductor light-emitting elements.The feature of semiconductor light-emitting elements, refer to small-sized and electrical efficiency good, can carry out luminous, the initial stage drive characteristic excellence of distinct color, and to vibration or conducting. disconnect the repeatability light a lamp strong, use semiconductor light-emitting elements at light emitting element lamp, owing to be semiconductor element, so need not worry the situation etc. of explosion etc.
Above-mentioned the 2nd light-emitting device is carried out the part of the light that the above-mentioned fluor of wavelength conversion radiates by will and hanging oneself from the part of the light of the interparticle above-mentioned excitation light source that sees through above-mentioned fluor by the light from above-mentioned excitation light source, mix and radiate, promptly can obtain to carry out the luminous light-emitting device of white color system.According to the 2nd light-emitting device, promptly can provide white color system luminous light-emitting device with higher luminous efficiency.For example, according to luminous element with blue light, and carry out the luminous of yellow ruddiness that nitride phosphor is excited, in addition, by carrying out the luminous of sodium yellow that fluor is excited, then according to the principle of the colour mixture of Guan Zaiguang, push between oxide based fluor and fluor and the blueness of coming system, the yellow ruddiness of nitride phosphor and the sodium yellow of fluor white and being discovered by the people.Herein, this light-emitting device is estimated light-emitting device very excellent on the class (Ra) in average color.Should on average show and estimate number (Ra) more than 80.Particularly estimate light-emitting device very excellent on the number (R9) in the special colour developing of the pointer that shows red composition.This special colour developing is estimated number (R9) more than 70.
The color designation of specification sheets kind and the relation of tristimulus coordinates are all according to JIS specification (JISZ 8110).
As above-mentioned, the of the present invention the 5th and the 6th nitride phosphor, all fabulous fluor of the characteristics of luminescence of brightness, quantum yield etc.The 2nd light-emitting device of the present invention can provide the light-emitting device of the white color system of the higher and reddish warm colour system of luminous efficiency.This light-emitting device on average develop the color estimate number (Ra), special colour developing is estimated number (R9) and is excellent light-emitting device.By providing blueness is the fluor of the luminous semiconductor light-emitting elements of light-emitting device, the near ultraviolet of luminous semiconductor light-emitting elements and nitride phosphor of the present invention combination, nitride phosphor of the present invention, green emitting and the light-emitting device of Yellow luminous fluor combination, and the luminous light-emitting device that carries out white or soft middle shade etc. promptly can be provided.Therefore, the present invention has the meaning of the technical elements of the light-emitting device that nitride phosphor can be provided and use this fluor.
As above-mentioned, nitride phosphor according to the of the present invention the 5th and the 6th, and at excitation light source when to use blueness be luminous semiconductor light-emitting elements, can provide according to this semiconductor light-emitting elements the irradiation of luminous light, and absorb its light and produce the nitride phosphor of the different light of (wavelength conversion) wavelength (having luminescent spectrum) at yellow to red area.Use the 3rd nitride phosphor that the light-emitting device of the luminous efficiency white color system that fabulous reddish warm colour is can be provided.
In addition, the luminous light-emitting device of the 2nd light-emitting device white color system of the present invention, this white on average the evaluation of demonstration property to count Ra be more than 80, show that particularly it is more than 70 that red special color developing is estimated number R9.The luminous light-emitting device of white color system of excellent color reproducing performance can be provided thus.
In addition, light-emitting device according to the multicolor of middle shade of the fluor of the of the present invention the 5th and the 6th nitride phosphor and blue-light-emitting, green emitting fluor, Yellow luminous fluor etc. being carried out blended measure more than a kind, promptly can provide reaching soft etc.
In addition, can provide with twilight sunset, particle diameter be controlled at decide the nitride phosphor of scope.
And then has a very important techniques meaning of the nitride phosphor that the raising that reaches the characteristics of luminescence, weather resistance can be provided.
In addition, for solving above-mentioned problem, the 7th～the 10th fluor of the present invention is at least a portion that absorbs the light with the 1st luminescent spectrum, and the light that will have 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum carry out luminous, and for the following fluor of forming.
The 7th fluor of the present invention is characterized in that: L-M-N: Eu wherein, WR system (L contain be selected from the group of being formed by the II valency of Be, Mg, Ca, Sr, Ba, Zn more than at least a kind.M contain be selected from the group of being formed by the IV valency of C, Si, Ge, Sn, Ti, ZR, Hf more than at least a kind.N nitrogen.The Eu europium.WR is the rare earth element except the Eu) fluor.According to the 7th fluor of the present invention, then can reach the raising of high brightness, high-quantum efficiency etc., luminous efficiency.In addition, can provide temperature profile fabulous fluor.In the 7th fluor, according to the combination of the system of rare earth element WR system of the Eu of activator and subsidy activator, to can be used as the merit of melting agent passable and reach secondary activation agent, and performance fusing assistant effect.The 7th fluor considers to reach according to this fusing assistant effect the raising of luminous efficiency, and to can be used as the merit of melting agent passable by reaching secondary activation agent, and the performance sensibilized, and reaches the raising of luminous efficiency.Sensitized fluorescence is meant and utilizes energy reception and registration effect and be purpose to improve luminous intensity, executes the auxiliary activation of sensitizing agent of body with forming energy.
The 7th fluor of the present invention, for example with the luminous source of luminous element or lamp etc. and the light of the 1st luminescent spectrum that radiates carries out wavelength conversion, and the light that will have the 2nd luminescent spectrum in the zone different with the 1st luminescent spectrum carries out luminous.
In addition, the 8th fluor of the present invention is characterized in that: wherein L-M-O-N: Eu, WR the system (L contain be selected from the group of being formed by the II valency of Be, Mg, Ca, Sr, Ba, Zn more than at least a kind.M contain be selected from the group of being formed by the IV valency of C, Si, Ge, Sn, Ti, ZR, Hf more than at least a kind.O is an oxygen.N is a nitrogen.Eu is an europium.Rare earth element except the WR system, Eu).The 5th fluor can use oxide compound at raw material.In addition, when making fluor, can consider also that in firing process oxygen contains in composition, and the 8th fluor of the present invention is in firing process, even in composition, contain aerobic, also can be so that the fluor of higher luminous efficiency to be provided.
The 9th fluor of the present invention is characterized in that: Ca-Si-N: Eu wherein, WR system, or Sr-Si-N: Eu, WR system, or Sr-Ca-Si-N: Eu, WR system (WR system is the rare earth element except the Eu) silicon nitride.Thus, can be provided in the fluor that long wavelength side has the 2nd luminescent spectrum.This principle is because the rayed that will have near the 1st luminescent spectrum of 460nm when fluor, then carry out the wavelength conversion of the 1st luminescent spectrum, and near the long wavelength side 580～700nm has the 2nd luminescent spectrum.In addition and in the same manner above-mentioned, be accompanied by the importing of secondary activation agent, and provide high-luminous-efficiency according to fusing assistant effect, sensitization effect.In addition, can provide tone different fluor according to auxiliary activation.X value and Y value according to chromaticity diagram determine tone.For example in the table 8, assisted the activatory fluor to be compared to, be displaced to more red-side not by auxiliary activatory fluor.When desire strengthened red composition, the 9th fluor of the present invention was very effective.And then can make short persistence and steady persistence according to auxiliary activation.For example, the light-emitting device that uses fluor is used when the indicating meter,, use so can be used as the fluor of short persistence because twilight sunset is shorter more preferred.
As the light that possesses the 1st luminescent spectrum, at the short wavelength side of 360～495nm, from the light of the luminous element with luminescent spectrum, light emitting element lamp etc.Originally mainly the blue based light-emitting device combination and the use of near luminescent spectrum are preferably to the 9th fluor with having 440～480nm.
On the other hand, the 2nd luminescent spectrum is according to the part of light with the 1st luminescent spectrum and excited fluophor, and the fluor that is excited carries out the spectrum of luminous light, and is positioned at the zone different with the 1st luminescent spectrum.The 2nd luminescent spectrum serves as preferred to have at least 1 peak wavelength near 560～700nm.
Fluor of the present invention has peak wavelength near 600～680nm.
The 10th fluor of the present invention is characterized in that: Ca-Si-O-N: Eu wherein, and WR system, or Sr-Si-O-N: Eu, W or Sr-Ca-Si-O-N: Eu, WR are silicon nitride.The 10th fluor uses oxide raw material and uses.In addition and in the same manner above-mentioned, be accompanied by the importing of secondary activation agent, and the fluor of high-luminous-efficiency is provided according to fusing assistant effect, sensitization effect.
In the 7th～the 10th fluor of the present invention,, serve as preferred more than at least a kind among Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, the Lu to contain as above-mentioned WR system.By Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu among the rare earth element that uses secondary activation agent, can provide luminous efficiency higher fluor.This is middle Y, La, no luminescence center such as Gd, Lu of considering rare earth element, and according to fusing assistant effect and sensitization effect.In addition, middle Pr, the Dy of consideration rare earth element, Tb, Ho, Er etc. have luminescence center, and according to fusing assistant effect and sensitization effect.
In the 7th～the 10th fluor of the present invention, the addition of above-mentioned WR system is that 10.0 weight % are following for preferred.When the concentration of system of the WR of the Eu of activator amount, secondary activation agent system forms institute when quantitatively above, owing to produce concentration delustring, and the reduction of luminous efficiency, so in above-mentioned scope, WR is preferred with the interpolation secondary activation agent.
In the of the present invention the 8th and the 10th fluor, the amount of above-mentioned O is for preferred below the 3.0 weight % to full composition amount.The of the present invention the 5th and the composition of the 7th fluor in contain aerobic.This is mainly to be contained in oxide compound is used when the situation of raw material, and oxide raw material is considered as and melts agent and work.When using this type of oxide raw material, more cheap owing to generally be compared to raw metal, so can lower raw materials cost.But the oxygen in the composition of fluor of the present invention also has the situation that reduces luminosity.Therefore, oxygen can be removed to the greatest extent is preferred outside system.So, relatively consider above-mentioned merits and demerits, and the oxygen concn in the composition of above-mentioned fluor determined in above-mentioned scope.But, even outside above-mentioned scope, because also can be to bring into play sufficient luminous efficiency, so be not limited to this scope.
In addition, the 7th～the 10th fluor of the present invention is added with Mn for preferred.In manufacturing processed, use the Sr-Ca-Si-N that adds Mn or Mn compound: Eu, during the fluor of WR system system, do not add the Sr-Ca-Si-N of Mn: Eu, the fluor of system of WR system more can reach the raising of the luminous efficiency of luminosity, quantum yield, energy efficiency etc.This is to consider that Mn or Mn compound are for promoting the Eu of activator 2+Diffusion, and particle diameter is increased, and reaches the cause of crystalline raising.In addition, with Eu 2+In the fluor as activator, consider Mn for working, and reach activator Eu as sensitizing agent 2+The cause of increase of luminous intensity.
When in the manufacturing process of above-mentioned the 7th～the 10th fluor, adding Mn or Mn compound, have also that Mn disperses in the operation of burning till, and in the composition of the fluor of final product, only contain the situation of addition Mn still less more originally.Therefore, in the composition of the fluor of final product, only add the Mn of use level amount still less originally for containing in composition.
Be added on the Mn of above-mentioned the 7th～the 10th fluor, usually with MnO 2, Mn 2O 3, Mn 3O 4, the oxide compound of MnOOH etc. or oxidizing water oxide compound and add, but be not limited to this, also can be Mn metal, Mn nitride, imide, acid amides or other inorganic salts, in addition, also can be for containing state in advance at other raw material.In addition, above-mentioned the 7th～the 10th fluor contains O in it is formed.O imports from the various Mn oxide compounds that constitute raw material, is considered to promote the Eu diffusion of Mn of the present invention, the effect that particle diameter is grown up, crystallinity improves.Also promptly, also can be even the effect that Mn adds changes over metal, nitride, oxide compound with the Mn compound to obtain identical effect, the effect when using oxide compound is bigger.Its result can produce the object of O in the composition of fluor that contains trace.Thus, even when use does not contain aerobic Mn compound person, and according to Eu 2O 3Deng other raw material, under the state of atmosphere etc. and import O, even and use when containing the compound of O, also can be to solve above-mentioned problem.
The addition of the Mn of above-mentioned the 7th～the 10th fluor has 0.01～0.3 mole for preferred to L (Sr-Ca, Sr, Ca etc.).Particularly, the addition of the Mn of above-mentioned fluor has 0.0025～0.03 mole for preferred to L (Sr-Ca, Sr, Ca etc.).By in raw material or in the manufacturing process, the measure with Mn is added on fluor promptly can reach the raising of the luminous efficiency of luminosity, energy efficiency, quantum yield etc.
In above-mentioned the 7th～the 10th fluor, the residual quantity of Mn is that 5000ppm is following for preferred.By Mn being added on the raising that above-mentioned fluor can reach luminous efficiency.Wherein, Mn is owing to disperse in the operation when burning till etc., thus be added in the raw material the Mn amount with make after composition in the Mn amount different.
In above-mentioned the 7th～the 10th fluor, serve as preferred more than at least a kind in the group of being formed by Fe to contain Mg, Sr, Ba, Zn, Ca, Ga, In, B, Al, Cu, Li, Na, K, Re, Ni, Cr, Mo, O and to be selected from.Element by containing Mg, B etc. at least promptly can reach the raising of the luminous efficiency of luminosity, quantum yield etc. in the measure of above-mentioned fluor.This reason is considered to constitute element at above-mentioned L-M-N: Eu by the composition that contains Mg, B etc., the substrate nitride phosphor of WR system etc., and the particle diameter of powder is become evenly and bigger, and obviously improve crystalline cause.Can carry out wavelength conversion with the part that high-level efficiency will have the light of the 1st luminescent spectrum by improving crystallinity, and obtain the fabulous fluor of luminous efficiency.In addition, by adding above-mentioned element, can adjust the persistence characteristic of fluor arbitrarily.As the display unit that the continuous demonstration of indicating meter, PDP etc. can repeat, its persistence characteristic promptly forms problem.With respect to this,, promptly can suppress twilight sunset by containing the measure at the substrate nitride phosphor such as micro-B, Mg, Cr, Ni, Al.Fluor of the present invention can be used display unit thus at indicating meter etc.In addition, in order to add B etc., even add as H 3BO 3Oxide compound, also unlikelyly reducing the characteristics of luminescence, and above-mentioned O shows that its important merit is passable also in diffusion process.So, constituting element by the composition with Mg, B etc. contains at above-mentioned silicon nitride, promptly can change particle diameter, crystallinity, the energy communicating path of fluor, absorption, reflection, scattering be changed and the characteristics of luminescence of the light-emitting device of the obtaining of luminous and light, twilight sunset etc. is changed.In other words, by adjusting this type of action, can be manufactured on the fluor that has the best characteristics of luminescence when constituting light-emitting device.
In addition, Sr, Ca, Ba etc. and L-M-N: Eu, the substrate nitride phosphor of system of WR system mixes and constitutes liquid crystal, by constituting liquid crystal, peak wavelength can be shifted in short wavelength side or long wavelength side.
Above-mentioned the 7th～the 10th fluor, its median size 3 μ m are above to be preferred.Do not add the Sr-Ca-Si-N of Mn: Eu, system of WR system, Sr-Si-N: Eu, system of WR system, Ca-Si-N: Eu, fluor, its median size of system of WR system are 1～2 μ m degree, and add the above-mentioned silicon nitride of Mn, its median size can be more than the 3 μ m.According to the difference of this particle diameter, then particle diameter is bigger, more can improve the luminosity of fluor, and has the advantage of the efficient that improves the light that takes out light-emitting device etc.
The 3rd light-emitting device of the present invention has at least:
Luminous element, its light that will have the 1st luminescent spectrum carries out luminous; And fluor, it absorbs at least a portion of the light of above-mentioned the 1st luminescent spectrum, and the light that will have 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum carries out luminous; It is characterized in that: above-mentioned fluor uses any of the 7th～the 10th fluor of the present invention.Can provide thus color and distinct colors with luminous element are carried out luminous light-emitting device.For example, the blueness of the pass by will assisting look and yellow, redness and blue-greenish colour, green and red-violet colour combination can provide white color system luminous light-emitting device.But, also can be not limited to white, and have the light-emitting device of the illuminant colour of expectation to provide.Particularly, the blue based light-emitting device that has near the 1st luminescent spectrum 440～480nm by use, the part of the light of the 1st luminescent spectrum is carried out wavelength conversion, and use light to carry out luminous Sr-Ca-Si-N: Eu with the 2nd luminescent spectrum of 600～660nm, the fluor of WR system system promptly can constitute and will make white blue based light-emitting device and luminous blueness system and the white color system that imposes the reddish warm colour of the yellowish red color light blended system of wavelength conversion through fluor are carried out luminous light-emitting device.
Use not only is limited to a kind at the fluor of the 3rd light-emitting device of the present invention, also can make up the fluor that has different peak wavelengths more than 2.For example, with respect to Sr-Ca-Si-N: Eu, the fluor of system of WR system has luminescent spectrum near 650nm, and Sr-Si-N:Eu, the fluor of system of WR system has luminescent spectrum near 620nm.By this being carried out the measure of desired amount blended, the desired location that promptly can be manufactured on the wavelength region of 620～650nm has the fluor of peak wavelength.Use these 2 kinds of fluor of combination fluor light-emitting device and only use the light-emitting device of a kind of fluor, can form different illuminant colours.The light-emitting device of the illuminant colour with expectation can be provided thus.
As above-mentioned the 7th～the 10th fluor of combination and the fluor that uses, the activated yttrium with cerium. aluminum oxide is fluor, with cerium activated yttrium. gadolinium. aluminum oxide is a fluor and with cerium activated yttrium. gallium. aluminum oxide be fluor serve as preferred more than any at least 1 or 2.As with cerium activated yttrium. aluminum oxide is that an example of fluor has Y 3Al 5O 12: Ce.As with cerium activated yttrium. gadolinium. aluminum oxide is that an example of fluor has (Y 0.8Gd 0.2) 3Al 5O 12: Ce.As with cerium activated yttrium. gallium. aluminum oxide is that an example of fluor has Y 3(Al 0.8Ga 0.2) O 12: Ce.By with the 7th～the 10th fluor of the present invention with cerium activated yttrium. aluminum oxide is that fluor etc. makes up with above-mentioned blue based light-emitting device, and the luminous light-emitting device of white color system of expectation promptly can be provided.From blue based light-emitting device with cerium activated yttrium. aluminum oxide is the combination of fluor and the light-emitting device that constitutes, show slightly blue white white, and because the white of warm colour system is not enough, so by containing fluor of the present invention, promptly can supply the colourity of warm colour system, and, promptly can provide the white color system light-emitting device of various colourities by suitably changing the use level of fluor.
As above-mentioned, the 3rd light-emitting device of the present invention has the meaning of the technical elements of the white color system light-emitting device that the fabulous reddish warm colour of luminous efficiency can be provided.In addition, also has the meaning of technical elements that yellow to the red area that can be provided in combined blue based light-emitting device etc. and use has the fluor of luminescent spectrum.
As above-mentioned, according to the 3rd light-emitting device of the present invention, the luminous efficiency white color system light-emitting device that fabulous reddish warm colour is promptly can be provided, also can have the fluor of luminescent spectrum in addition, and then have the meaning of the very important techniques aspect of the fluor that the raising that reaches weather resistance can be provided to be provided at yellow to the red area that uses with combination such as blue based light-emitting device.
In addition, in order to solve above-mentioned problem, relate to the fluor of I1 of the present invention～I3, absorb at least a portion of the light with the 1st luminescent spectrum, and the light that will have 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum carries out luminously, and is made of following silicon nitride.
II fluor of the present invention is characterized in that: the Sr-Ca-Si-N that wherein adds Mn: R is a silicon nitride.Herein, the rare earth element more than 1 or 2 of Eu is contained at least in R system.Thus, promptly can be provided at the fluor that long wavelength side has the 2nd luminescent spectrum.Also promptly, near the rayed of the 1st luminescent spectrum the 460nm when the fluor of II, is then carried out the light wavelength conversion of the 1st luminescent spectrum, and the light that will near the long wavelength side 580～700nm has the 2nd luminescent spectrum carries out luminous.
In manufacturing process, add the Sr-Ca-Si-N of Mn and Mn compound: R is the fluor of silicon nitride, be compared to the fluor that the Sr-Ca-Si-N that does not add Mn: R is a silicon nitride, more can improve the luminous efficiency of luminosity, quantum yield, energy efficiency etc.This is because consider (the Eu for example of R system of Mn or Mn compound promoted activator 2+) diffusion, and can reach that particle diameter increases and crystalline raising.In addition, with (the Eu for example of R system 2+) in the fluor as activator, consider Mn for working as sensitizing agent, and reach the increase of the luminous intensity of activator R system.Sensitized fluorescence refers to utilize energy reception and registration effect and is purpose to improve luminous intensity, executes the sensitizing agent of body and makes the activatory state of assisting and will constitute energy.
Herein, the 1st luminescent spectrum for example comes the short wavelength side of comfortable 360～495nm to have the light of the luminous element, luminous element electricity etc. of luminescent spectrum.The luminous element of this wavelength domain has near the blue based light-emitting device of the luminescent spectrum 440～480nm for preferred.On the other hand, the luminescent spectrum of the wavelength region may that the 2nd luminescent spectrum is different with the 1st luminescent spectrum according at least a portion of the light of the 1st luminescent spectrum and excited fluophor, and makes the fluor that has been excited carry out the luminescent spectrum (wavelength conversion) of luminous light.Its at least 1 part of the 2nd luminescent spectrum, and near 560～700nm, have peak wavelength for preferred.II fluor of the present invention has peak wavelength near 600～680nm.
On address the fluor of silicon nitride described later, though in this manufacturing process, add Mn and Mn compound, Mn disperses in firing process, and, only contain the situation of the more micro-Mn of addition more originally also by in the forming of the fluor of the silicon nitride of final product.Therefore, in the composition of the fluor of the silicon nitride of final product, add originally use level still less.
The 12nd fluor of the present invention is characterized in that: the Sr-Si-N that wherein is added with Mn: R is a silicon nitride.The silicon nitride that is somebody's turn to do also in manufacturing process, more can improve luminous efficiency by adding when Mn promptly can not add Mn.Mn to Sr-Si-N: R be the effect of silicon nitride with above-mentioned identical, promote (the Eu for example of R system of activator with Mn 2+) diffusion, increase particle diameter, and reach crystalline raising and in the fluor of R system as activator that be considered, Mn works as sensitizing agent, and can reach the increase of the luminous intensity of activator R system.Sr-Si-N of the present invention: R is the silicon nitride fluor, and having with above-mentioned Sr-Ca-Si-N: R is the different composition and the luminescent spectrums of fluor of silicon nitride, and has peak wavelength near 610～630nm.
The 13rd fluor of the present invention is characterized in that: the Ca-Si-N that wherein is added with Mn: R is a silicon nitride.Effect when adding Mn is with above-mentioned identical.Wherein, add the Ca-Si-N of Mn: R is a silicon nitride, has peak wavelength near 600～620nm.
Be added on the Mn of the silicon nitride that constitutes the 11st～the 13rd above-mentioned fluor, usually with MnO 2, Mn 2O 3, Mn 3O 4, the oxide compound of MnOOH etc. or oxidizing water oxide compound and add, but be not limited to this, also can be Mn metal, Mn nitride, imide, acid amides or other inorganic salts, in addition, also can be for containing state in advance at other raw material.Above-mentioned silicon nitride contains O in it is formed.O imports from the various Mn oxide compounds that constitute raw material, and considers that Mn according to the present invention promotes the diffusion of activator R system, the effect that grain is grown up, crystallinity improves.Also promptly, the effect that Mn adds, even when the Mn compound changed over metal, nitride, oxide compound, also can be to obtain identical effect.Effect when in addition, using oxide compound is bigger.Its result promptly can produce the object that contains micro-O in the composition of silicon nitride.Therefore, the substrate nitride phosphor forms Sr-Ca-Si-O-N: R system, Sr-Si-O-N: R system, Ca-Si-O-N: R system.Thus, even when the Mn compound uses the person that do not contain the aerobic, also according to Eu 2O 3Deng other raw material, atmosphere etc. and import O, even and use the compound that contains O, also can grow up and crystallinity improves with the diffusion, the grain that promote activator R system by Mn.
The amount of above-mentioned O is for preferred below the 3 weight % to full composition amount.Can reach the raising of luminous efficiency thus.
Above-mentioned silicon nitride contain Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mo, Cr and in the group that Ni formed more than at least a kind for preferred.Constitute element by the composition that contains Mn, Mg, B etc. at above-mentioned silicon nitride at least, promptly can reach the raising of the luminous efficiency of luminosity, quantum yield etc.This reason is considered to constitute element by the composition that contains Mn, B etc. at above-mentioned substrate nitride phosphor, and the particle diameter of powder is become evenly and bigger, and obviously improves crystallinity.Expeditiously the 1st luminescent spectrum is carried out wavelength conversion by improving crystallinity, and make fluor with the 2nd fabulous luminous spectrum of luminous efficiency.In addition, can adjust the persistence characteristic of fluor arbitrarily.Can show continuously and the display unit that repeats that as indicating meter, PDP etc. its persistence characteristic forms problem.Therefore, by containing micro-B, Mg, Cr, Ni, Al etc., promptly can suppress twilight sunset at the substrate nitride phosphor.Fluor of the present invention can be used display unit thus at indicating meter etc.In addition, the additive of Mn, B etc. is even add MnO 2, Mn 2O 3, Mn 3O 4Or H 3BO 3Deng oxide compound, also unlikelyly reducing the characteristics of luminescence, and as above-mentioned O also in diffusion process, it is passable to demonstrate important merit.So, constitute element at above-mentioned silicon nitride by the composition that contains Mn, Mg, B etc., promptly can change particle diameter, crystallinity, the energy communicating path of fluor, and change the taking-up that absorbs, reflects, disperses and make luminous and light, the characteristics of luminescence of the light-emitting device of twilight sunset etc. changes.Utilize this promptly can make the fluor that can utilize when light-emitting device, and make preferably and change.
Sr-Ca-Si-N: R is a silicon nitride, and the mol ratio of Sr and Ca is that Sr: Ca=1～9: 9～1 is for preferred.Particularly, Sr-Ca-Si-N: R is a silicon nitride, and the mol ratio of Sr and Ca is Sr: Ca=1: 1 for preferred.By changing the mol ratio of Sr and Ca, promptly the 2nd luminescent spectrum can be shifted in long wavelength side.In table 501 described later, has Sr: Ca=9: 1, Sr: Ca=1: the fluor of 9 composition, to peak wavelength is 624nm, 609nm, mol ratio with Sr and Ca changes over Sr lentamente: Ca=7: 3, Sr: Ca=6.4 and Sr: Ca=3.7, Sr: during Ca=4.6, promptly peak wavelength can be shifted in peak wavelength is 639nm, 643nm and 636nm, 642nm and long wavelength side.So, promptly can be manufactured on the fluor that long wavelength side more has peak wavelength.And then when changing the mol ratio of Sr and Ca, promptly can be manufactured on Sr: Ca=1: 1 o'clock, peak wavelength was the fluor that 644nm and long wavelength's measuring tool have peak wavelength.In addition, by changing the mol ratio of Sr and Ca, promptly can reach the raising of luminosity.Table 1 is with Sr: Ca=9: 1 o'clock the characteristics of luminescence makes 100%.When Sr is increased the molar weight of Ca, promptly can reach Sr: Ca=1: the raising of 9 o'clock 170.3% and 70.3% luminosity.In addition, by changing the mol ratio of Sr and Ca, promptly can reach the raising of quantum yield.Shown in the table 501, Sr: Ca=9: 1 o'clock 100% quantum yield, for reaching Sr: during Ca=5.5 167.7% and the raising of quantum yield.So, promptly can reach the raising of luminous efficiency by changing the mol ratio of Sr and C.
The use level of the activator R system of above-mentioned fluor, it is preferred that Sr-Ca, Ca are 0.003～0.5 mole.Particularly, the use level of the activator R of above-mentioned fluor system, it is preferred that Sr-Ca, Sr, Ca are 0.005～0.1 mole.Peak wavelength can be shifted in long wavelength side by the use level that changes activator R system.In addition, can reach the raising of the luminous efficiency of luminosity, quantum yield etc.Table 16 described later is to the test-results of 18 expressions with the use level change of the R system of the silicon nitride of Sr-Ca-Si-N: R system.In the table 16, as at Sr: Ca=7: in 3, when Sr-CaR is 0.005 mole, peak wavelength is that 624nm, luminosity are 100%, to quantum yield is 100%, and peak wavelength was 637nm when R was 0.03 mole, and luminosity is 139.5%, quantum yield is 199.2% o'clock, and then the characteristics of luminescence forms fabulous state.
The addition of the Mn of above-mentioned fluor, it is preferred that Sr-Ca, Sr, Ca are 0.001～0.3 mole.Particularly, the addition of above-mentioned fluor Mn to Sr-Ca, Sr, Ca be 0.0025～0.03 mole for preferred.In raw material or in the manufacturing process,, promptly can reach the raising of the luminous efficiency of luminosity, energy efficiency, quantum yield etc. by Mn being added on the fluor of silicon nitride.Table 19 described later is to the test-results of 23 expressions with the addition change of the Mn of the silicon nitride of Ca-Si-N: R system.Table 19 is to 23 being benchmark with the fluor of the silicon nitride that do not have to add Mn for example, and when luminosity is 100%, quantum yield was made 100% o'clock, then Ca was added the fluor of silicon nitride of 0.015 mole Mn, luminosity is 115.3%, and quantum yield is 117.4%.So, promptly can reach the raising of the luminous efficiency of luminosity, quantum yield etc.
Above-mentioned fluor constitutes with the combination arbitrarily of the 11st fluor and the 12nd fluor, the 12nd fluor and the 13rd fluor, the 11st fluor and the 13rd fluor preferably.For example, the fluor that constitutes by the combination of the 11st fluor and the 12nd fluor, refer to Sr-Ca-Si-N: R is that the fluor and the Sr-Si-N of silicon nitride: R is the fluor blended fluor of silicon nitride.For example with respect to Sr-Ca-Si-N: R is the fluor of silicon nitride, has luminescent spectrum near 650nm, then Sr-Si-N: R is the fluor of silicon nitride, has luminescent spectrum near 620nm.Mix action by this being carried out desired amount, the desired location that promptly can be manufactured on the wavelength region of 620～650nm has the fluor of peak wavelength.Be not limited to aforesaid combination herein, also can make Sr-Ca-Si-N: R is that the fluor and the Ca-Si-N of silicon nitride: R is the fluor blended fluor of silicon nitride, is that the fluor and the Sr-Si-N of silicon nitride: R is that the fluor and the Ca-Si-N of silicon nitride: R is the fluor blended fluor of silicon nitride with Sr-Ca-Si-N: R.This type of combination also can have the fluor of peak wavelength with the desired location of the wavelength region that is manufactured on 600～680nm.
The the 11st～the 13rd fluor of the present invention is characterized in that: median size is that the above fluor of 3 μ m is for preferred.Not adding the Sr-Ca-Si-N of Mn: R system, Sr-Si-N: R system, Ca-Si-N: R is the fluor of silicon nitride, and its median size is 1～2 μ m degree, and adds the above-mentioned silicon nitride of Mn, and its median size is more than the 3 μ m.According to the difference of this particle diameter, have particle diameter when big then luminosity improve, and light takes out the advantage of efficient rising etc.
The the 11st～the 13rd fluor of the present invention, the residual quantity 5000ppm of its Mn is following to be preferred.By Mn being added on the 11st～the 13rd fluor of the present invention, promptly can obtain above-mentioned effect.But, because Mn dispersed burning till when handling etc., thus be added in the raw material the Mn amount with make after composition in the Mn amount different.
The 4th light-emitting device of the present invention has at least:
Luminous element, its light that will have the 1st luminescent spectrum carries out luminous; And
Fluor, it absorbs at least a portion of the light of above-mentioned the 1st luminescent spectrum, and the light that will have 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum carries out luminous (carrying out wavelength conversion); It is characterized in that:
Above-mentioned fluor uses the 11st～the 13rd fluor of the present invention.For example, the blue based light-emitting device that has near the 1st luminescent spectrum 440～480nm by use, and carry out the wavelength conversion of the 1st luminescent spectrum, and use the fluor of the present invention of the 2nd luminescent spectrum with 600～660nm, promptly can provide from blue based light-emitting device and luminous blueness system and mix, and carry out the luminous light-emitting device of white color system of reddish warm colour system according to the yellowish red color light that fluor carries out wavelength conversion.
Above-mentioned fluor is to contain with cerium activated yttrium. and aluminum oxide is fluor, with cerium activated yttrium. gadolinium. aluminum oxide is a fluor and with cerium activated yttrium. gallium. aluminum oxide is that fluor serves as preferred.As cerium activated yttrium. aluminum oxide is that an example of fluor has Y 3Al 5O 12: Ce.As with cerium activated yttrium. gadolinium. aluminum oxide is that an example of fluor has (Y 0.8Gd 0.2) 3Al 5O 12: Ce.As with cerium activated yttrium. gallium. aluminum oxide is that an example of fluor has Y 3(Al 0.8Ga 0.2) 5O 12: Ce.By with fluor of the present invention with cerium activated yttrium. aluminum oxide is fluor etc. and above-mentioned blue based light-emitting device combination, and the luminous light-emitting device of white color system of expectation promptly can be provided.By blue based light-emitting device with cerium activated yttrium. aluminum oxide is the light-emitting device that combines formation of fluor, show slightly blue white white, and because the white of warm colour system is not enough, so by containing fluor of the present invention, promptly can supply the colourity of warm colour system, and, promptly can provide the white color system light-emitting device of various colourities by suitably changing the use level of fluor.
As above-mentioned, the 4th light-emitting device of the present invention has the meaning of the technical elements of the white color system light-emitting device that the fabulous reddish warm colour of luminous efficiency can be provided.In addition, also has the meaning of technical elements that yellow to the red area that can be provided in combined blue based light-emitting device etc. and use has the fluor of luminescent spectrum.
In addition, in order to solve above-mentioned problem, the 14th nitride phosphor of the present invention, it is characterized in that: contain nitrogen at least, and absorb at least a portion of the light with the 1st luminescent spectrum, and the light that will have 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum carries out luminous
Above-mentioned nitride phosphor is characterized in that: with L XM YN (2/3X+4/3Y): R system (L be selected from the group of being formed by the II valency of Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg more than at least a kind, M be selected from the group of being formed by the IV valency of C, Si, Ge, Sn, Ti, ZR, Hf more than at least a kind, R is an activator) represented, and contain be selected from the group of forming by Mg, Sr, Ba, Zn, Ca, Ga, In, B, Al, Cu, Mn, Li, Na, K, Re, Ni, Cr, Mo, O and Fe more than at least a kind.Above-mentioned the 14th nitride phosphor can reach the raising of the luminous efficiency of luminosity, energy efficiency, quantum yield etc. by having the composition element of Mn, B etc.This reason is considered to constitute element by the composition that contains Mn, B etc., and the particle diameter of powder can be become evenly and bigger, and can obviously improve crystallinity.Passing through like this improved crystallinity and can be expeditiously the light of the 1st luminescent spectrum be carried out wavelength conversion, and makes the fabulous nitride phosphor of luminous efficiency.In addition, the 14th nitride phosphor of the present invention can be adjusted persistence characteristic arbitrarily.Can show continuously and the display unit that repeats that as indicating meter, PDP etc. its persistence characteristic becomes problem, and B, Mg by containing trace, Cr, Ni, Al etc. promptly can suppress twilight sunset at above-mentioned the 14th nitride phosphor.Nitride phosphor of the present invention can be used display unit thus at indicating meter etc.So, contain element that the substrate nitride phosphor at fluor comprised and the element different by interpolation with this element, and change particle diameter, crystallinity, the energy communicating path of fluor and change the taking-up of absorption, reflection, deployment conditions, luminous and light, and the characteristics of luminescence of the light-emitting device of twilight sunset etc. suffers great influence.
Above-mentioned the 14th nitride phosphor is with L XM YN (2/3X+4/3Y): R system (L be selected from the group of being formed by the II valency of Mg, Ca, Sr, Ba more than at least a kind, MSi, R is an activator) represented, and to contain to be selected from the group of being made up of Mg, Sr, Ba, Zn, B, Al, Cu, Mn, Cr, O and Ni serve as preferred more than at least a kind.By L being made Mg, Ca, Sr, Ba and by M is made Si, promptly can provide to be difficult for decomposing, and reliability is higher and nitride phosphor that crystallinity is fabulous.The light-emitting device of life characteristic fabulous (life-span is long) meanwhile, promptly can be provided.Utilize the 14th nitride phosphor and carry out luminous light source as light and when the wavelength of 400～460nm has the blue led of peak value and constitutes light-emitting device, promptly can be manufactured near the luminous light-emitting device of white color system that has peak wavelength 560～680 the 1st luminescent spectrum.
With the represented activator of above-mentioned R, Eu is preferred.Promptly can absorb near the light of the 1st luminescent spectrum 250～480nm thus, and can make different with the 1st luminescent spectrum fluor that have the 2nd luminescent spectrum of peak value at yellow to red area that particularly have according to this absorption.
Particularly, in the time of will having the rayed that is excited at the 1st luminescent spectrum of 460nm at the 14th nitride phosphor, promptly can be provided near the nitride phosphor that shows maximum wavelength 580 to 620nm.Thus, by with blue led and the 14th nitride phosphor of the present invention combination, promptly can provide white color system luminous light-emitting device.
With the represented activator of above-mentioned R, contain Mn, B, Ce, Mg, Cu, Al and Eu in more than at least a kind for preferred.Thus, promptly can be provided at and only use Eu different zone when the promoting agent to show the fabulous nitride phosphors of the characteristics of luminescence such as maximum wavelength.
Above-mentioned X and YX=2, Y=5 are preferred.Also promptly, the substrate nitride phosphor is with L 2M 5N 8: R is represented to be preferred.Can provide crystallinity fabulous nitride phosphor thus.But, because the part of L is with the replacement of R system, so the total mole number of L and R system becomes X=2.Also promptly, R 0.03The time, the substrate nitride phosphor is with L 1.97R 0.03M 5N 8Expression.
Above-mentioned X and YX=1, Y=7 are preferred.Also promptly, the substrate nitride phosphor is with LM 7N 10: R is represented.Can provide crystallinity fabulous nitride phosphor thus.
Above-mentioned L and above-mentioned R have L: R=1: the pass of 0.001～1 mol ratio is for preferred.By with L XM YN (2/3X+4/3Y): the cooperation ratio of the R system in the represented substrate nitride phosphor of R is made above-mentioned scope, can obtain the nitride phosphor of high brightness.In addition, also can be to provide temperature profile fabulous nitride phosphor.More preferably make L: R=1: the pass of 0.03～0.05 mol ratio.This mol ratio promptly can provide high brightness and temperature profile fabulous nitride phosphor when this scope.In addition, because the compound high price of the Eu of raw material so pass through the proportioning of the compound of minimizing Eu, promptly can be made cheaper fluor.
Above-mentioned the 14th nitride phosphor, the size of its median size 0.1～10 μ m is preferred.During as the situation of the light-emitting device of LED or LED lamp, preferably the fluorescence thickness roughly is directly proportional in median size, and the particle diameter little then coating amount of healing can more lack.On the other hand, the general big particle diameter person of luminous efficiency is for bigger.According to the present invention, luminosity, energy efficiency, the fabulous nitride phosphor of the characteristics of luminescence that quantum yield is higher promptly can be provided, also can be easy to handle and reduce the nitride phosphor of coating amount simultaneously to provide.
In above-mentioned the 14th nitride phosphor, the 2nd luminescent spectrum is preferred at the peak value that yellow to red area has more than 1 at least.By having the nitride phosphor combination of the 2nd luminescent spectrum, promptly can provide the luminous light-emitting device of white color system of warm colour system with blue led with at yellow to red area.
It is preferred that above-mentioned the 2nd luminescent spectrum has more than 1 with the peak value at least in the wavelength region of 520nm to 780nm.By having the ultraviolet of peak value or the nitride phosphor combination of blue LE and the 2nd luminescent spectrum of wavelength region, promptly can provide the luminous light-emitting device of white color system of warm colour system at 400～460nm with 570nm to 730nm.
The 2nd manufacture method of nitride phosphor of the present invention is with L XM YN (2/3X+4/3Y): (L is selected from by Be R, Mg, Ca, Sr, Ba, Zn, Cd, in the group that the II valency of Hg is formed more than at least a kind, M is selected from by C, Si, Ge, Sn, Ti, Zr, in the group that the IV valency of Hf is formed more than at least a kind, R is an activator) represented, and contain and be selected from by Mg, Sr, Ba, Zn, Ca, Ga, In, B, Al, Cu, Mn, Li, Na, K, Re, Ni, Cr, Mo, the manufacture method of the nitride phosphor more than at least a kind in the group that O and Fe formed is characterized in that: have in ammonia atmosphere the operation that the raw material with above-mentioned nitride phosphor burns till.In firing process, use the nitrogen that contains several % hydrogen usually as reducing gas, but owing to hydrogen meeting etch crucible, stove material etc., so promptly contained in fluor is formed by the crucible material of etch.The crucible material that contains in fluor is formed becomes impurity, and causes the reason of the luminous efficiency reduction that causes luminosity, quantum yield, energy efficiency etc.Therefore,, promptly the etch crucible can be prevented, and the higher fluor of luminous efficiency free from foreign meter can be made by in ammonia atmosphere, burning till.In addition, reactivity can be improved in the ammonia atmosphere, and the high fluor of yield rate can be produced.
Above-mentionedly burn till the crucible that handle to use the boron nitride material and burn till to preferably.Molybdenum crucible has the anxiety that obstruction is luminous and the obstruction reaction is united.On the other hand, when using the crucible of boron nitride material, because unlikely hindering luminous and the reaction system, so can make the nitride phosphor of extreme high purity.In addition, because the crucible of boron nitride material decomposes in hydrogen nitrogen, so can't use burning till in hydrogen and nitrogen gas atmosphere.
The 5th light-emitting device of the present invention has at least:
Semiconductor light-emitting elements, its light with the 1st luminescent spectrum carries out luminous; And
Fluor, it absorbs at least a portion of the light of above-mentioned the 1st luminescent spectrum, and the light of the 2nd luminescent spectrum that will be different with above-mentioned the 1st luminescent spectrum carries out luminous; It is characterized in that:
Above-mentioned fluor contains the 14th nitride phosphor of the present invention.So processing then can constitute the luminous light-emitting device of white color system of warm colour system.
Above-mentioned fluor and then contain activated yttrium with cerium. aluminum oxide is that fluor serves as preferred.By containing the YAG fluorescent substance, promptly can be adjusted to the illuminant colour of expectation.Using blue led and YAG is the light-emitting device of fluor, bag degree coordinate X=0.348, Y=0.367, colour temperature 4939K, can find that the white white color system of indigo plant is luminous during with visual inspection.With respect to this, using blue led and the 14th nitride phosphor is the light-emitting device of fluor blended fluor with YAG, tristimulus coordinates X=0.454, Y=0.416, and colour temperature 2828K can find during with visual inspection that the white color system that warm colour is is luminous.By using such blue led and the 14th nitride phosphor and YAG is the light-emitting device of fluor blended fluor, and the white color system light-emitting device that eyes is had the warm colour system of soft sense promptly can be provided.The light-emitting device of bulb look particularly, can be provided.In addition, being not limited to YAG is fluor, by the fluor combination that semiconductor light-emitting elements and the characteristics of luminescence is extremely excellent, promptly can provide can carry out indigo plant, green, red outside, versicolor luminous light-emitting device.
Contain above-mentioned fluor with above-mentioned cerium activated yttrium. aluminum oxide is the weight ratio of fluorescent substance and above-mentioned nitride phosphor, is mixed into preferred with 1～15 pair 1.By changing YAG is the use level of fluor and above-mentioned nitride phosphor, promptly can carry out the fine adjustment of colour temperature.Particularly, by taking above-mentioned cooperation ratio, promptly can provide to carry out the luminous light-emitting device of white color system of the fabulous warm colour system of luminous efficiency.
Above-mentioned the 1st luminescent spectrum has luminescence peak at 360～550nm, and the fluor that is excited by at least a portion because of the light of above-mentioned the 1st luminescent spectrum the part of light of luminous light and above-mentioned the 1st luminescent spectrum mix and radiate carry out white color system luminous for preferably.Can use the 1st luminescent spectrum have excitation wavelength EX=460nm emission wavelength blue led outside, also can be so that with the ultraviolet LED of emission wavelength with excitation wavelength EX=400nm.Ultraviolet LED is not a visible rays, and owing to people's (eyes) can't feel because of electric current changes the luminous subtle change that produces, so there is not colour-change.Nitride phosphor of the present invention, owing to absorb near the light of the emission wavelength 360～480nm, so can use the ultraviolet LED of EX=400nm.Therefore, by and near 360～550, have the 1st luminescent spectrum of luminescent spectrum light carry out the combination of luminous fluor, the light-emitting device of white color system can be provided.
Above-mentioned fluor is powder or plastochondria, and contains at the light translucent material for preferred.Thus, promptly can carry out the inching of illuminant colour easily, and can improve luminous efficiency.
Above-mentioned semiconductor light-emitting elements is that III group-III nitride based compound semiconductor light-emitting device is for preferred.Thus, promptly can improve luminosity, and can provide reliability higher light-emitting device.When covering all or part of of semiconductor light-emitting elements with nitride phosphor of the present invention, can use same material and suppress the deterioration that the border face produced, the retroaction of nitride phosphor and semiconductor light-emitting elements, each problem of peeling off etc.
It is 74 to 94 that number Ra is estimated in the average colour developing of above-mentioned light-emitting device, and colour temperature is that 200K to 800K is for preferred.The white color system light-emitting device of warm colour system can be provided thus.In particular for the preferred color of choice temperature is 3000K to 5000K, and the light-emitting device of bulb look can be provided.The light-emitting device of reddish white color system can be provided by the value that improves special color developing R9 in addition.
As above-mentioned, the present invention has the light-emitting device of the white color system that reddish warm colour system can be provided, and can provide with combination such as blue L ED and use have the meaning of technical elements of the nitride phosphor of luminescent spectrum at yellow to red area.
Therefore, the invention provides the higher fluor of luminosity, particularly, use is carried out ultraviolet to the light of the luminescent spectrum of blue region to light source and is carried out luminous semiconductor light-emitting elements, and will carry out so-called tone reversal, and can provide the fluor of the luminous excellent in luminous characteristics of the white color system of reddish warm colour system from the light of this semiconductor light-emitting elements.In addition, can provide twilight sunset short fluor.Advance to provide the luminous light-emitting device of white color system is carried out in the combination of blue semiconductor luminous element and above-mentioned fluor.
The 14th fluor of the present invention, can use at fluorescent display tube, indicating meter, PDP, CrT, FL, FED and projection tube etc., particularly with blue series LED or ultraviolet light-emitting diode luminescent lamp as the illumination of the demonstration usefulness in the light-emitting device of light source, shop, illumination of medical on-the-spot usefulness etc.In addition, also can be applied in the field of backlight, the photodiode (LED) of portable phone.
So, the present invention can solve insurmountable in the past problem, and has the meaning of extremely excellent technical elements.
In addition, in order to solve above-mentioned problem, the 3rd manufacture method of nitride phosphor of the present invention, be to contain nitrogen at least, and absorb at least a portion of the light with the 1st luminescent spectrum, and the light that will have 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum carries out the manufacture method of luminous nitride phosphor, it is characterized in that:
Has the operation of in ammonia atmosphere, burning till.
The manufacture method of fluor in the past (for example be documented in the world and openly number 01/40403) after more the raw material of purified parent, activator etc. mixes, is loaded to molybdenum crucible, and the operation through burning till in stove.
Be documented in the method for this international publication number 01/40403, under the mixed-gas atmosphere of hydrogen (3.75%) and nitrogen (4001/h) and the operation of burning till.With respect to this, manufacture method of the present invention is carried out in ammonia atmosphere, and thus, it is high promptly can to produce yield rate, and shows the fluor of the characteristics of luminescence of higher high brightness.
Will be referred to the embodiment of the 3rd manufacture method of the present invention and the comparative result of comparative example (comparative example 10) and be shown in table 32 (being described in detail in the working of an invention mode).In the table 32, remove the operation of burning till, compare the processing of burning till of example 10 and the embodiment that relates to the 3rd manufacture method of the present invention with identical condition.Comparative example 10 burns till in hydrogen and nitrogen atmosphere, and embodiments of the invention burn till in ammonia atmosphere.Its result, with respect to comparative example 10 and the brightness of embodiments of the invention reaches 18% unexpectedly, this brightness of high 18% improves the very excellent effect of expression, and the meaning of the aspect that possesses skills.In addition, energy efficiency also improves 17.6%.And then quantum yield improves 20.7%.By these results, provable by through manufacturing process of the present invention, promptly can reach the supply of stable article of fluor of the characteristics of luminescence of the high and exhibit high brilliance of yield rate, and the manufacture method of making the fabulous nitride phosphor of efficient can be provided.And then manufacturing method according to the invention, promptly can make the fabulous nitride phosphor of temperature profile.
Firing process of the present invention burns till under the temperature condition of 1200～1600 ℃ scope to preferably.1200～1400 ℃ scope more preferably.Firing process of the present invention, 1200～1400 ℃ scopes and through the firing process that carries out 1 stage that a few hours burn till for preferred, but also can through since 700～1000 ℃ carry out the 1st of a few hours and burn till, and then heat up and carry out the 2 stage firing process that the 2nd of a few hours burn till at 1200～1400 ℃.
In above-mentioned nitride phosphor, the 2nd luminescent spectrum is preferred at the peak value that yellow to red area has more than 1 at least.When fluor has such luminescent spectrum, promptly can constitute the luminous light-emitting device of white color system with blue series LED combination.More preferably the 2nd luminescent spectrum has peak value more than 1 for the Huang-red area in the wavelength region of 580～630nm.
Above-mentionedly burn till the crucible that uses the boron nitride material and burn till to preferably.The document of being quoted uses molybdenum crucible.Molybdenum crucible has the anxiety that obstruction is luminous and reaction is united.On the other hand, when using boron nitride crucible of the present invention, owing to can not hinder luminous and the reaction system, so can make the nitride phosphor of extreme high purity.In addition, boron nitride crucible is owing to decomposing in hydrogen nitrogen, so the synthetic method of citing document can't be used hydrogen and nitrogen gas atmosphere.
Above-mentioned nitride phosphor has with L XM YN (2/3X+4/3Y): R system (L be selected from the group of being formed by the II valency element of Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg more than at least a kind, M be selected from the group of being formed by the IV valency element of C, Si, Ge, Sn, Ti, ZR, Hf more than at least a kind, R is an activator) represented basic comprising is for preferred.The nitride phosphor of high brightness, energy-efficient, high electronic efficiency can be provided thus.In the nitride phosphor except with L XM YN (2/3X+4/3Y): outside the substrate nitride phosphor that R is represented, also residual containing in impurities in raw materials.For example Co, Mo, Ni, Cu, Fe etc.The active reason that causes reducing luminosity and hinder activator owing to this type of impurity is so can remove to the greatest extent system outside to preferably.
Above-mentioned nitride phosphor has with L XM YN (2/3X+4/3Y): R system (L be selected from the group of being formed by the II valency element of Mg, Ca, Sr, Ba more than at least a kind, Si, R are activator) represented basic comprising is for preferred.This nitride phosphor uses and will carry out luminous blue series LED at the light that 400～460nm has the 1st luminescent spectrum of peak value, then near 560～680nm, have peak wavelength when being radiated at nitride phosphor of the present invention, and can make the luminous light-emitting device of white color system by colour mixture.
The operation that this manufacture method has the compound of the nitride of the nitride of L, M and R system is preferred.It is few promptly can to produce yield rate thus, and makes the fabulous nitride phosphor of efficient.This blended operation is in that to burn till the behavior of advancing preferred, but also can with in burning till, burn till the back and mix and burn till again.The molar ratio of each element that compound cooperated of the nitride of the L of raw material or synthetic intermediate, the nitride of M and R, the compound of the nitride of the nitride of L: M: R=1.80～2.20: 4～6: 0.01～0.10 is preferred.Can obtain more uniform fluor thus.
The above-mentioned activator of representing with R is that Eu serves as preferred.With L XM YN ((2/3X)+(4/3Y): in the represented basic comprising of R, by using near the light (light of 1st luminescent spectrum) of Eu promoting agent absorbs 250～480nm.Can carry out the light of 2nd luminescent spectrum different luminous according to this absorption with the light of the 1st luminescent spectrum.Particularly, can constitute the luminous light-emitting device of white color system by with blue series LED and nitride phosphor of the present invention combination.
Above-mentioned L and above-mentioned R have L: the pass of the mol ratio of R system=1: 0.001～1 is preferred.By will be with L XM YN ((2/3X)+(4/3Y): the cooperation ratio of the R in the represented substrate nitride phosphor of R promptly can obtain the nitride phosphor of high brightness as above-mentioned scope.In addition, can provide temperature profile fabulous nitride phosphor.It more preferably then is L: R=1: the relation of 0.003～0.05 mol ratio.When high scope, promptly can provide high brightness, and the fabulous nitride phosphor of temperature profile.In addition, because the compound price height of the Eu of raw material so pass through the cooperation ratio of the compound of minimizing Eu, promptly can be made cheaper fluor.
According to the nitride phosphor of making by manufacture method of the present invention, promptly can provide the nitride phosphor of the characteristics of luminescence of exhibit high brilliance, energy-efficient, high-quantum efficiency etc.In addition, can provide temperature profile fabulous nitride phosphor.
The 6th light-emitting device of the present invention is to have at least:
Semiconductor light-emitting elements, its light with the 1st luminescent spectrum carries out luminous; And
Nitride phosphor, it contains nitrogen at least, and absorbs at least a portion of the light of above-mentioned the 1st luminous spectrum, and the light of the 2nd luminescent spectrum that will be different with above-mentioned the 1st luminescent spectrum carries out luminous; Light-emitting device, it is characterized in that:
The nitride phosphor that above-mentioned nitride phosphor the 3rd manufacture method according to the present invention is made.So, by semiconductor light-emitting elements and the extremely combination of excellent fluor of the characteristics of luminescence, then except blue, green, red, can provide and to carry out versicolor luminous light-emitting device.Particularly can provide the market requirement bigger, the light-emitting device that reddish white color system is luminous.
The alkaline-earth metal silicon nitride fluor of one example of nitride phosphor of the present invention absorbs short wavelength's the light of 250～450nm of visible region, and reflects with the long wavelength of 580～650nm.
For example, according to blue series LED and alkaline-earth metal silicon nitride fluor of the present invention are made up, and be radiated at the formation of alkaline-earth metal silicon nitride fluor of the present invention as the part of the light that blue series LED is luminous, promptly can make the light-emitting device of reddish white color system.Also can be with blue series LED, in the past Y 3Al 5O 12The mixture of fluor and alkaline-earth metal silicon nitride fluor of the present invention combination and using also can obtain the visible light of white portion with the mixing of the visible light of the visible light by blue region and Huang-orange areas thus.From the above, the present invention has the nitride phosphor and the manufacture method thereof of the excellent in luminous characteristics that high brightness, energy-efficient, high-quantum efficiency etc. can be provided, in addition, provide the meaning of often carrying out luminous stable light-emitting device and having the technical elements that the manufacture method of making the fabulous nitride phosphor of efficient can be provided.
According to the present invention, promptly can provide luminosity higher fluor, particularly, be used in light source and have the photodiode of ultraviolet to the luminescent spectrum of blue region, and will be, and carry out the fluor of the luminous excellent in luminous characteristics of white color system from the light conversion of this photodiode.In addition, it is higher to reach yield rate, and the providing of the stable goods of the fluor of the characteristics of luminescence of exhibit high brilliance, and can provide and make the fabulous manufacture method of efficient.Advance to provide blue series LED is carried out the luminous light-emitting device of white color system with this fluor combination.So, the present invention can solve insurmountable problem in the past, and has the meaning of extremely excellent technical elements.
In order to solve above-mentioned problem, of the present inventionly relate to a kind of light-emitting device, be to have:
Luminous element;
The 1st fluor, it absorbs from least a portion of the light of this luminous element and carries out the light of different wavelength luminous; And
The 2nd fluor, it absorbs from least a portion of the light of this luminous element and carries out the light of different wavelength luminous; Light-emitting device, it is characterized in that:
The peak wavelength that possesses the luminescent spectrum of this luminous element possesses the peak wavelength of excitation spectrum of above-mentioned the 1st fluor and the peak wavelength that possesses the excitation spectrum of above-mentioned the 2nd fluor and compares more long wavelength side.The light-emitting device of the generation that can suppress chroma offset promptly can be provided thus.Particularly, owing to this light-emitting device produces chroma offset along the track of blackbody radiation, thus be compared in the situation that vertically produces chroma offset in the direction of the track of blackbody radiation, in people's vision, the less chroma offset of perceiving.In addition, because of the interaction of the 1st fluor and the 2nd fluor, and make the amplitude of hue shift become very narrow.
Above-mentioned luminous element along with the increase of current density, and transfers at short wavelength side the peak wavelength of the luminescent spectrum that possesses above-mentioned luminous element.When increasing the input electric current of luminous element, then producing current density increases, and the peak wavelength of the luminescent spectrum that possesses luminous element is transferred at short wavelength side.Utilize this effect and the light-emitting device that can prevent chroma offset is provided.
The 1st above-mentioned fluor and above-mentioned the 2nd fluor are along with the variation of the surrounding temperature of the 1st fluor and the 2nd fluor and change of luminous intensity is preferred about equally.By making such formation, promptly can provide according to the variation that increases the surrounding temperature that produces along with the input electric power of fluor, make the 1st fluor of launching efficiency generation change and the temperature profile of the 2nd fluor roughly become identical, even and surrounding temperature changes, also can be with the light-emitting device of the generation that suppresses chroma offset.Particularly, can provide the chroma offset that produces according to increase and the interaction of the chroma offset that produces because of the variation of the surrounding temperature of fluor, and more can suppress the light-emitting device of the generation of chroma offset because of the current density of luminous element.
The variation of the surrounding temperature of above-mentioned the 1st fluor and the 2nd fluor mainly is that the variation of the input electric current of the past above-mentioned luminous element of basis produces.By making such formation, promptly can form influence because of the temperature of coming self-emission device causes the 1st fluor that launching efficiency changes and the temperature variation of the 2nd fluor roughly to become identical, even and the surrounding temperature of fluor changes, also can be with the light-emitting device of the generation that suppresses chroma offset.
The peak wavelength of above-mentioned luminous element luminescent spectrum is that 350nm to 530nm is for preferred.Particularly has the 400nm to 530nm of tone for preferred at the light that comes self-emission device.By such formation, i.e. the tonal variation of the tonal variation of may command semiconductor light-emitting elements and fluor, and can control all chroma offset of light-emitting device.
In the scope of the wavelength change of the luminous element that above-mentioned the 1st fluor is produced with the current density change of above-mentioned luminous element the time, the launching efficiency of the short wavelength side longer wavelength side of the scope of this wavelength change is higher, in other words, relate to luminous because of the fluor that exciting light produced of the short wavelength side of luminous element, the higher light-emitting device of luminous its luminous intensity of the fluor that produces because of the exciting light of the long wavelength side of luminous element.Thus, when increasing the current density of luminous element, then the luminous intensity of the 1st fluor also increases.In addition, as the back narration, the luminous intensity of the 2nd fluor also increases.Therefore, can provide the light-emitting device that extremely can suppress hue shift.
In the scope of the wavelength change of the luminous element that above-mentioned the 1st fluor is produced with the current density change of above-mentioned luminous element the time, at the short wavelength side of the scope of this wavelength change, the peak wavelength that possesses the excitation spectrum with the 1st fluor is for preferred.The peak wavelength of the luminescent spectrum of luminous element is positioned at the position that exciting of the 1st fluor absorbs the largest peaks wavelength, and it is luminous the 1st fluor to be carried out thus full blast, and Beam Control that can light-emitting device is all becomes maximum.
Above-mentioned the 1st fluor contains Y and Al, and contain be selected from least a element among Lu, Sc, La, Gd, Tb, Eu and the Sm and be selected from Ga and In in a kind of element, and contain the yttrium that is activated to be selected from least a element in the rare earth element. aluminium. garnet is that fluor serves as preferred.By taking such formation,, and then can make the light-emitting device of the relative reduction that can suppress all light beams [Im] of the light-emitting device that produces because of heating even then surrounding temperature changes and also can suppress the generation of chroma offset.Above-mentioned yttrium. aluminium. garnet is that the peak wavelength 420nm to 470nm that excites absorption spectrum of fluor is preferred.By taking such formation, promptly can form and be compared to prior art it dwindles because of the chroma offset that drops into electric current and produce, and more can improve the light-emitting device of color developing.
Possess above-mentioned the 1st fluor excitation spectrum peak wavelength and possess the difference of peak wavelength of the luminescent spectrum of above-mentioned luminous element, 40nm is following to be preferred.By taking such formation, promptly can form than prior art and dwindle the chroma offset that it produces because of the input electric current, and can improve the light-emitting device of color developing.
In the scope of the wavelength change of the luminous element that above-mentioned the 2nd fluor is produced with the current density change of above-mentioned luminous element the time, the short wavelength side longer wavelength side of the scope of this wavelength change and launching efficiency is higher, in other words, relate to the luminous of fluor that the exciting light because of the short wavelength side of luminous element produces, the fluor that produces because of the exciting light of the long wavelength side of luminous element is luminous, and the higher light-emitting device of its luminous intensity.Thus, when increasing the current density of luminous element, then the luminous intensity of the 2nd fluor also increases.In addition, as above-mentioned, the luminous intensity of the 1st fluor also increases.Therefore, can provide the light-emitting device that extremely can suppress hue shift.
Above-mentioned the 2nd fluor contains N, and contain at least a element that is selected among Be, Mg, Ca, Sr, Ba and the Zn and at least a element in C, Si, Ge, Sn, Ti, ZR and Hf, and to contain the nitride phosphor that is activated with at least a element in rare earth element serve as preferred.By taking such formation,, and then can make the light-emitting device of the reduction that can suppress all light beams [Im] of the light-emitting device that produces because of heating even then surrounding temperature changes and also can suppress the generation of chroma offset.In addition, above-mentioned the 2nd fluor is that the light of 350～600nm excites that to carry out luminous fluor serve as preferred with wavelength.By taking such formation, promptly can form and be compared to prior art and dwindle it because of dropping into the chroma offset that electric current produces, and can improve the light-emitting device of color developing.
Above-mentioned light-emitting device is preferred as backlight liquid crystal display light source or illumination light source.By taking such formation, even its chroma offset of variation that promptly can form because of surrounding temperature is compared to liquid-crystal display or the illumination light source of prior art for being difficult for producing.
In order to reach the 3rd above-mentioned purpose, light-emitting device of the present invention is possessing light source and is absorbing the light that will have different wavelength from least a portion of the light of this light source and carry out in luminous a plurality of fluor, it is characterized in that above-mentioned fluor contains:
The 1st fluor, it possesses on the light source of at least one; And
The 2nd fluor, its at least a portion of carrying out luminous light are to be absorbed in more than above-mentioned the 1st fluor at least a;
And more above-mentioned the 2nd fluor of above-mentioned the 1st fluor more possesses the side at above-mentioned light source.
By taking such formation, promptly can make the light-emitting device that is compared to prior art and more improves its color developing.
In addition, of the present invention the 101st is bright, and the 100th the light-emitting device according to the present invention, above-mentioned the 2nd fluor are on above-mentioned at least one light source, and/or with this on light source of different at least one of at least one light source.
Like this pass through to use a plurality of led chips, and directly excite the fluor that covers led chip respectively, promptly can make compared with prior art and can improve color developing, and can carry out the light-emitting device of high brightness luminescent.
In addition, invention of the present invention the 102nd, the 100th to 101 the light-emitting device according to the present invention, above-mentioned light-emitting device has:
The 1st recess, it loads above-mentioned the 1st fluor and the light source of at least one; And
The 2nd recess, it contains the 1st recess, and loads above-mentioned the 2nd fluor and the light source of at least one.
By taking such formation, promptly can make the light-emitting device that more improves color developing.
In addition, invention of the present invention the 103rd, the the 100th to 102 the light-emitting device according to the present invention, above-mentioned the 1st fluor contains N, and contain at least a element that is selected among Be, Mg, Ca, Sr, Ba and the Zn and at least a element in C, Si, Ge, Sn, Ti, ZR and Hf, and contain the nitride phosphor that is activated with at least a element in rare earth element.
By taking such formation, promptly can make the light-emitting device that more improves its color developing.
In addition, invention of the present invention the 104th, the the 100th to 103 the light-emitting device according to the present invention, above-mentioned the 2nd fluor contains Y and Al, and contain at least one element that is selected among Lu, Sc, La, G, Tb, Eu and the Sm and an element in Ge and In, and contain the yttrium that is activated with at least a element in rare earth element. aluminium. garnet is a fluor.
By taking such formation, promptly can make the light-emitting device that more improves color developing.
In addition, invention of the present invention the 105th, the 100th to 104 the light-emitting device according to the present invention, the luminous output reduced rate that above-mentioned the 2nd fluor rises with respect to temperature be with above-mentioned the 1st fluor about equally.
By taking such formation, promptly can make and compared with prior art improve its color developing, even and surrounding temperature change, also can be with the light-emitting device of the generation of the reduction that suppresses light beam [Im] or chroma offset.
In addition, invention of the present invention the 106th, the 100th to 105 the light-emitting device according to the present invention, above-mentioned light source semiconductor light-emitting elements.
By taking such formation, promptly can make and compared with prior art improve its color developing, and low consumption electric power and small-sized light-emitting device.
In addition, invention of the present invention the 107th, the the 100th to 106 the light-emitting device according to the present invention, above-mentioned light source semiconductor light-emitting elements with absorb from least a portion of the light of this semiconductor light-emitting elements and will have the light source that the light of different wavelength carries out luminous fluor combination.
By taking such formation, promptly can make and compared with prior art improve its color developing, and low consumption electric power and small-sized light-emitting device.
In addition, invention of the present invention the 108th, the 100th to 107 the light-emitting device according to the present invention, above-mentioned light source luminescent spectrographic peak wavelength is 350nm to 530nm.
By taking such formation, promptly can make the light-emitting device that more improves color developing.
In addition, invention of the present invention the 109th, the 1st to 108 the light-emitting device according to the present invention, above-mentioned light-emitting device backlight liquid crystal display light source or illumination light source.
By taking such formation, promptly can make and more improve color developing, even and surrounding temperature change and be compared to liquid-crystal display or the illumination light source that prior art is difficult for producing color shift.
In addition, invention of the present invention the 110th, the 100th to 10 the light-emitting device according to the present invention excites the luminous light source of above-mentioned the 1st fluor and excites the light of above-mentioned the 2nd fluor and the luminous output of luminous light source, can distinguish independence and controls.
By taking such formation, promptly can make the light-emitting device of the colour temperature of free adjustment mixed light.
[description of drawings]
Fig. 1 is the sectional view that expression relates to the light-emitting device of type i of the present invention.
Fig. 2 is orthographic plan (A) and the sectional view (B) that expression relates to the light-emitting device of Type II of the present invention.
Fig. 3 is the sectional view of light-emitting device that expression relates to the type-iii of cabinet-type of the present invention.
Fig. 4 is the schema of manufacturing process of the nitride phosphor of expression embodiments of the present invention 1.
Fig. 5 is the figure of the luminescent spectrum of expression when exciting the nitride phosphor of embodiments of the invention 60 with Ex=460nm.
Fig. 6 is the figure of excitation spectrum of the fluor of expression embodiment 60.
Fig. 7 is the figure of reflection spectrum of the fluor of expression embodiment 60.
Fig. 8 is the figure of tristimulus coordinates of the light-emitting device of expression embodiments of the invention 81.
Fig. 9 is the figure of the luminescent spectrum of expression when exciting the nitride phosphor of embodiments of the invention 86 with the light of wavelength Ex=460nm.
Figure 10 is the figure of excitation spectrum of the nitride phosphor of expression embodiment 86.
Figure 11 is the figure of reflection spectrum of the nitride phosphor of expression embodiment 86.
Figure 12 A, Figure 12 B are the SEM photos of taking the nitride phosphor of embodiment 86.
Figure 13 is the schema of manufacturing process of the fluor of expression embodiments of the present invention 3.
Figure 14 is relatively with substrate nitride phosphor Ca-Si-N: Eu, and the activator WR system of system of WR system carries out the graphic representation of luminosity of fluor of the embodiment 110 to 124 of various changes.
Figure 15 is that expression is measured substrate nitride phosphor Ca-Si-N: Eu, and the interpolation concentration of the activator La of La is carried out the figure of measurement result of luminosity of fluor of the embodiment 125 to 133 of various changes.
Figure 16 be expression with substrate nitride phosphor Ca-Si-N: Eu, the interpolation concentration of the activator La of La is carried out the figure of luminescent spectrum of fluor of the embodiment 127 to 129 of various changes.
Figure 17 be expression with substrate nitride phosphor Ca-Si-N: Eu, the interpolation concentration of the activator La of La is carried out the figure of reflection spectrum of fluor of the embodiment 127 to 129 of various changes.
Figure 18 be expression with substrate nitride phosphor Ca-Si-N: Eu, the interpolation concentration of the activator La of La is carried out the figure of excitation spectrum of fluor of the embodiment 127 to 129 of various changes.
Figure 19 A takes embodiment 128, and Figure 19 B is SEM (scanning electron microscope) photo of taking the fluor of embodiment 129.
Figure 20 is the figure of tristimulus coordinates of the light-emitting device of expression embodiments of the invention 167.
Figure 21 is the figure of manufacture method of the fluor of expression embodiments of the present invention 4.
Figure 22 is the figure of the luminescent spectrum of expression when exciting the fluor of embodiments of the invention 173 with Ex=460nm.
Figure 23 represents the figure of excitation spectrum of the fluor of embodiment 173.
Figure 24 is the figure of reflection spectrum of the fluor of expression embodiment 173.
Figure 25 is the figure of the luminescent spectrum of expression when exciting the fluor of embodiment 170 to 176 with Ex=460nm.
Figure 26 is the figure of the luminescent spectrum of expression when exciting the fluor of embodiment 177,178,180,181,182,184,190,191,193 with Ex=460nm.
Figure 27 A takes embodiment 205, and Figure 27 B is SEM (scanning electron microscope) photo of taking the fluor of embodiment 206.
Figure 28 is the figure of luminescent spectrum of the light-emitting device of expression embodiments of the invention 221.
Figure 29 is the figure that the color developing of the light-emitting device of expression embodiment 221 is estimated.
Figure 30 is the figure of luminescent spectrum of the light-emitting device of expression embodiments of the invention 222.
Figure 31 is the figure that the color developing of the light-emitting device of expression embodiment 222 is estimated.
Figure 32 is the figure of tristimulus coordinates of the light-emitting device of expression embodiments of the invention 222.
Figure 33 is the schema of manufacturing process of the nitride phosphor of expression embodiments of the present invention 5.
Figure 34 is the figure of the luminescent spectrum of expression when exciting the nitride phosphor of embodiment 225 and 226 with Ex=460nm.
Figure 35 is the figure of the excitation spectrum of expression embodiment 225 and 226 nitride phosphor.
Figure 36 is the figure of the reflection spectrum of expression embodiment 225 and 226 nitride phosphor.
Figure 37 is SEM (scanning electron microscope) photo of the nitride phosphor of embodiment 226.
Figure 38 is the figure of the luminescent spectrum of expression when exciting the nitride phosphor of embodiment 224 and comparative example 7 with Ex=460nm.
Figure 39 is the figure of the luminescent spectrum of expression when exciting the nitride phosphor of embodiment 231 with Ex=460nm.
Figure 40 is the figure of measurement result that measures the residual opticity of embodiment 233.
Figure 41 is the figure of luminescent spectrum of the light-emitting device of expression embodiments of the invention 245.
Figure 42 is the figure of tristimulus coordinates of the light-emitting device of expression embodiment 245.
Figure 43 is the schema of manufacturing process of the fluor of expression embodiments of the present invention 6.
Figure 44 is the figure of the luminescent spectrum of expression when exciting embodiment 247 and comparative example 10 with Ex=460nm.
Figure 45 is expression excites 248,249 o'clock luminescent spectrum of embodiment with Ex=460nm figure.
Figure 46 is the figure of the excitation spectrum of expression embodiment 248,249.
Figure 47 is the figure of the reflection spectrum of expression embodiment 248,249.
Figure 48 is expression excites 251,252 o'clock luminescent spectrum of embodiment with Ex=400nm figure.
Figure 49 is expression excites 251,252 o'clock luminescent spectrum of embodiment with Ex=460nm figure.
Figure 50 is the figure of the reflectivity of expression embodiment 251 and 252.
Figure 51 is the figure of the excitation spectrum of expression embodiment 251 and 252.
Figure 52 is the figure of the luminescent spectrum of expression when exciting embodiment 254 with Ex=460nm.
Figure 53 is the figure of luminescent spectrum of the light-emitting device of expression embodiments of the invention 256.
Figure 54 represents the figure of tristimulus coordinates of the light-emitting device of embodiment 256.
Figure 55 is the sectional view of model utility of the photodiode of one embodiment of the invention.
Figure 56 is the figure of the electric current-relative luminosity spectral characteristic of the led chip of expression one embodiment of the invention.
Figure 57 is that the YAG of expression one embodiment of the invention is the figure that excites absorption spectrum of fluor.
Figure 58 is that the YAG of expression one embodiment of the invention is the figure of the luminescent spectrum of fluor.
Figure 59 is the figure that excites absorption spectrum of the nitride phosphor of expression one embodiment of the invention.
Figure 60 is the figure of luminescent spectrum of the nitride phosphor of expression one embodiment of the invention.
Figure 61 is the figure of the surrounding temperature-colorimetric properties (according to the mensuration of pulsed drive) of expression one embodiment of the invention.
Figure 62 is the figure of the electric current-colorimetric properties (according to the mensuration of pulsed drive) of expression one embodiment of the invention.
Figure 63 is the figure of the electric current-colorimetric properties (according to the mensuration of DC driving) of expression one embodiment of the invention.
Figure 64 is the figure of light output characteristic of surrounding temperature-relatively of the fluor 1 of expression one embodiment of the invention.
Figure 65 is the figure of light output characteristic of surrounding temperature-relatively of the fluor 2 of expression one embodiment of the invention.
Figure 66 is the figure of light output characteristic of surrounding temperature-relatively of the fluor 3 of expression one embodiment of the invention.
Figure 67 is the figure of light output characteristic of surrounding temperature-relatively of the fluor 4 of expression one embodiment of the invention.
Figure 68 is the figure of light output characteristic of surrounding temperature-relatively of the fluor 5 of expression one embodiment of the invention.
Figure 69 is that the YAG of expression one embodiment of the invention is the figure that excites absorption spectrum of fluor.
Figure 70 is that the YAG of expression one embodiment of the invention is the figure of the luminescent spectrum of fluor.
Figure 71 is the figure that excites absorption spectrum of the nitride phosphor of expression one embodiment of the invention.
Figure 72 is the figure of luminescent spectrum of the nitride phosphor of expression one embodiment of the invention.
Figure 73 is the figure of the electric current-colorimetric properties (according to the mensuration of DC driving) of expression one embodiment of the invention.
Figure 74 is the sectional view of the model utility of photodiode of the present invention.
Figure 75 is the sectional view of the model utility of photodiode of the present invention.
Figure 76 is the sectional view of the model utility of photodiode of the present invention.
Figure 77 is the sectional view of the model utility of photodiode of the present invention.
Figure 78 is the top view (78A) and the sectional view (78B) of the model utility of photodiode of the present invention.
Figure 79 is the figure of the luminosity spectral characteristic of expression light-emitting device of the present invention.
Figure 80 is expression in order to the figure of the luminosity spectral characteristic of the light-emitting device of the prior art that compares with the present invention.
Figure 81 is the figure of the luminosity spectral characteristic of expression led chip of the present invention.
Figure 82 is that expression YAG of the present invention is the figure that excites absorption spectrum of fluor.
Figure 83 is that expression YAG of the present invention is the figure of the luminescent spectrum of fluor.
Figure 84 is the figure that excites absorption spectrum of expression nitride phosphor of the present invention.
Figure 85 is the figure of the luminescent spectrum of expression nitride phosphor of the present invention.
Figure 86 is the figure of expression electric current-colorimetric properties of the present invention (according to the mensuration of DC driving).
Figure 87 is the figure of light output characteristic of the expression surrounding temperature of using the photodiode of fluor 261-1 of the present invention-relatively.
Figure 88 is the figure of light output characteristic of the expression surrounding temperature of using the photodiode of fluor 261-2 of the present invention-relatively.
Figure 89 is the figure of light output characteristic of the expression surrounding temperature of using the photodiode of fluor 266-1 of the present invention-relatively.
Figure 90 is the figure of light output characteristic of the expression surrounding temperature of using the photodiode of fluor 266-2 of the present invention-relatively.
Figure 91 is the figure of light output characteristic of the expression surrounding temperature of using the photodiode of fluor 266-3 of the present invention-relatively.
Figure 92 is that excite the YAG of embodiment 7 with Ex=460nm be the fluor (figure of the luminescent spectrum during fluor 7-1～7-4) in expression.
Figure 93 is the figure of the reflection spectrum of expression fluor 7-1～7-4.
Figure 94 is the figure of the excitation spectrum of expression fluor 7-1～7-4.
Figure 95 is the figure of the excitation spectrum of expression fluor 7-5.
Figure 96 is the figure of the excitation spectrum of expression fluor 7-6.
Figure 97 is the figure of expression luminescent spectrum when excited fluophor 7-5 and fluor 7-6 with Ex=460nm.
Among the figure,
1 sapphire substrate
2 semiconductor layers
3 electrodes
4 projections
5,10,101,202 luminous elements
11,8a fluor
12 coating members
13,13a, 13b lead frame
14,110 electroconductibility electric wires
15,204 modular units
16 walls
102,309 lead-in wire electrodes
103 insulated enclosure materials
104,110,203,310 leads
105 substrates
106 lead-in wires
107 glass port portions
108 fluor
109 colour switching portions
200,300,400 photodiodes
201 coating portions
202,302,304 led chips
205,402 lead-in wire is installed
206,401 inner leads
301 the 1st recesses
303 the 2nd recesses
305 the 1st luminescent coatings
306 the 2nd luminescent coatings
308 encapsulation
[embodiment]
Below, use embodiment and embodiment, fluor of the present invention and manufacture method thereof are described.But the present invention is not limited to this embodiment and embodiment.
Light-emitting device of the present invention, it possesses at least:
Luminous element, it has the 1st luminescent spectrum; And
Fluor, it absorbs the light of at least a portion of the 1st luminescent spectrum, and the light that will have the 2nd luminescent spectrum carries out luminous;
Wherein, use distinctive fluor of the present invention as this fluor.
Concrete example (all formations) with reference to this light-emitting device of description of drawings.
(the light-emitting device I of Class1)
The light-emitting device I of Class1 is constructed as follows:
Luminous element 10, its contain sapphire substrate 1, stacked in the above semiconductor layer 2 and be formed on positive and negative electrode 3 (positive and negative electrode 3 is formed on the same one side side on the semiconductor layer 2) on its semiconductor layer 2;
Lead frame 13a, 13b, its positive and negative electrode 3 by luminous element conducts electricity respectively with conducting wire 14 and is connected;
Coating member 12, it contains the fluor 11 in lead frame 13a is arranged on integrally formed cup with the state of periphery that can covering luminous element 10; And
Modular unit 15, it covers all.
Also have, in luminous element 10, the semiconductor layer 2 on the sapphire substrate 1 is provided with luminescent layer (not shown), and the luminescent spectrum of the light of exporting from this luminescent layer has peak wavelength at ultraviolet to blue region (below the 50nm).
The light-emitting device I of the type 1, for example following mode and making.
In addition, luminous element 10 is set in shifting coupling, and with electrode up (surface upwards) at the lead frame 13a and the joint (following) that are provided with cup.After engaging, the frame 13 that draws that is engaging luminous element is transferred to the lead shifting coupling, with gold thread negative potential 3 leads of luminous element 10 are bonded on the set guiding 13a of cup, positive electrode 3 leads are bonded on the opposing party's lead frame 13b.
Then, be transferred to modular device, and fluor 11 and coating member 12 be injected in the cup of lead frame 13 with dispenser.Fluor 11 and coating member 12 are mixed into the ratio of expectation in advance equably.
Inject after the fluor 11, be immersed in lead frame 13 in the modular type frame that is injected with modular unit 15 in advance after, unload the mo(u)ld bottom half frame and make resin solidification, promptly can make the light-emitting device I of bullet cut as shown in Figure 1.
(the light-emitting device II of type 2)
With reference to Fig. 2 the light-emitting device II that relates to the type 2 different with the light-emitting device I of Class1 is described.
The light-emitting device of the light-emitting device II surface installing type of the type 2.Various luminous elements be can use as luminous element 101 herein, for example, the nitride semiconductor luminescent element of ultraviolet, blue nitride semiconductor luminescent element also can be used.This luminous element 101 of sentencing ultraviolet illustrates for example.
Luminous element 101 (led chip 101) has the semi-conductive nitride semiconductor luminescent element of InGaN that peak wavelength is about 370nm as luminescent layer.Component structure as LED stacks gradually on sapphire substrate: the n type AlGaN layer of the n type GaN layer of the adulterated nitride-based semiconductor of ammonia, the adulterated nitride-based semiconductor n of GaN, the ammonia type GaN layer that constitutes the n type contact layer be formed with Si doped n type electrode, nitride-based semiconductor, have the luminescent layer of the single quantum well structure of InGaN layer, as the AlGaN layer that is doped with the p type coating of Mg, be doped with the GaN layer of the p type contact layer of Mg.Also have, on sapphire substrate, be formed with the GnN layer with low temperature as buffer layer.In addition, the p N-type semiconductorN is after film forming, to carry out anneal more than 400 ℃.In addition, the same one side side of each contact layer surface of pn being exposed the nitride-based semiconductor on sapphire substrate according to etching mode, and on the n type contact layer of having exposed, electrode is formed band shape, and roughly comprehensive in p type contact layer is formed with the light transmission p electrode of being made up of metallic film.And then on light transmission p electrode, use sputtering method and and electrode be formed with base electrode abreast.
Put among the II sending out of form 2, encapsulation is owing to base stage 105 and the fernico making line 106 that central part has the fernico system of the recess of taking in luminous element 101 constitutes.This base stage 105 is inserted with to air hermetic the lead-in wire electrode 102 of fernico system respectively in the both sides of recess, and fernico making line 106 is provided with glass port portion 107 at central part.In addition, be formed with the Ni/Ag layer on the surface of base stage 105 and lead-in wire electrode 102.
The light-emitting device II of type 2 uses the encapsulation that is as above constituted and makes with following operation.
At first, with the Ag-Sn alloy above-mentioned led chip 101 is bonded in the recess as the above-mentioned and base stage 105 that constitutes.
Then, each electrode of the led chip 101 that will engage with Ag lead 104 is respectively done being connected of electric property with the electrode 102 that respectively goes between that exposes in the recess bottom surface of base stage 105.
Then, after the moisture in the recess of base stage 105 is got rid of fully, the fernico making line 106 of central part by will having glass port portion 107 cover carry out sealing weld carry out close former.Set in advance colour switching portion (the coating portion of containing fluor 108) 109 at the back side of glass port oral area 107 herein.This colour switching portion 109 will be added with the Ca of B in advance 2Si 5N 8: Eu, (Y 0.8Gd 0.2) Al 5O 12: the fluor 108 of Ce etc. contains by nitrocotton 90wt% and R system-aluminum oxide 10wt% and in the slurry of forming, and the slurry coating that will contain fluor is at the back side of the light transmission window portion 107 of lead-in wire 106, and forms by carrying out being heating and curing in 30 minutes in 220 ℃.So handle and the light-emitting device II of formation, can carry out the luminous photodiode of the white color system of high brightness.In addition, root is the light-emitting device II of type 2 thus, and the light-emitting device of the very simple and property produced in batches of chroma control, reliability excellence promptly can be provided.
In addition, light-emitting device II as the type 2 of above-mentioned formation, component parts all can be made inorganics, even and the luminous making ultraviolet region that radiates from led chip 101 or the short wavelength zone of visible light, also can constitute the more light-emitting device of high reliability to have effect ground.
(the light-emitting device III of type 3)
Fig. 3 represents the sectional view of formation of the light-emitting device III of type 3 of the present invention, and this light-emitting device III is the light-emitting device of type at interval.
In Fig. 3, with the identical parts of parts of the light-emitting device I of Class1, give identical symbol and represent, and omit its explanation.
Light-emitting device III passes through on the surface of the modular unit 15 of light-emitting device I, is covered with by the wall 16 that fluor (figure) dispersive photopermeability resin is constituted to constitute.Wall 16 is evenly dispersed in the photopermeability resin with fluor.The photopermeability resin that will contain this fluor be entrenched in light-emitting device I modular unit 15 shape and be shaped.In addition, also can be with after in the photopermeability resin that will contain fluor is infused in institute's formed frame, light-emitting device I is pressed into to this type frame and the manufacture method of moulding, to replace chimeric mode.As the concrete material of the translucidus resin of wall 16, use the temperature profile of Resins, epoxy, urea-formaldehyde resin, silicone resin etc., the transparent resin that has excellent weather resistance, silicon sol, glass, inorganic binder etc.Outside above-mentioned, can use the thermosetting resin of melamine resin, stupid phenol resins etc.In addition, also can use the thermoplastic rubber etc. of thermoplastic resin, stupid ethene one butadienecopolymer of polyethylene, polypropylene, polyvinyl chloride, poly-stupid ethene etc., the urethane of fragmentation etc.In addition, also can close fluor and all contain diffusant, barium titanate, titanium oxide, aluminum oxide etc.In addition, also can contain Photostabilised dose or tinting material.Use is at the fluor of wall 16, the distinctive fluor of standby the present invention described later.Also can in the cup that lead-in wire 13a is installed, use fluor of the present invention.But because fluor is used at wall 16, in the cup that lead-in wire 13a is installed, it is also passable only to deposit coating member 12.
So and the light-emitting device III that constitutes, the part of the light of its self-emission device 10 and radiation by wall 16 time, is carried out wavelength conversion according to fluor.The light of wavelength conversion like this and the light that do not carry out the blueness of wavelength conversion according to fluor are mixed, its result, the light of white is radiated to the outside from the surface of wall 16.
Below, the fluor that relates to embodiments of the present invention is described.
Embodiment 1
Fluor of the present invention is characterized in that: it is with general formula L XM YN ((2/3) X+ (4/3) Y): R system or L XM YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): the nitride phosphor that R is represented, and this nitride phosphor to contain with above-mentioned L, above-mentioned M, above-mentioned O, above-mentioned N, above-mentioned and R be different element (below, abbreviate " different element " as)
Herein, L be selected from the II family element of forming by Mg, Ca, Sr, Ba, Zn more than at least a kind,
The middle Si that M is selected from C, Si, Ge be in the necessary IV family element more than at least a kind,
The middle Eu that R is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Lu be in the necessary rare earth element more than at least a kind.
In the general formula, X, Y and Z are greatly at 0 numerical value arbitrarily.Particularly X and YX=2, Y=5 or X=1, Y=7 are preferred.Particularly, will be with (Sr TCa 1-T) 2Si 5N 8: Eu, Sr 2Si 5N 8: Eu, Ca 2Si 5N 8: Eu, Sr TCa 1-T2Si 7N 10: Eu, SrSi 7N 10: Eu, Ca 2Si 5N 8: represented nitride phosphor such as Eu uses as the substrate nitride phosphor to preferably.Then, this substrate nitride phosphor contain with above-mentioned L, above-mentioned M, above-mentioned O, above-mentioned N, above-mentioned be different elements with R.This difference element is selected from by Li, Na, K, R is b, Cs, Cu, Ag, the I family element that Au formed, by B, Al, Ga, the iii group element that In formed, by Ti, ZR, Hf, Sn, the IV family element that Pb formed, by P, Sb, the V group element that Bi formed, by the VI family element that S formed, by V, Nb, the V group element that Ta formed, by Cr, Mo, the VI family element that W formed, by the VII family element that Re formed, by Fe, Co, IR system, Ni, Pd, Pt, R is the element more than at least a kind in the group VIII element formed of u.This type of different elements 1 or contain at nitride phosphor more than 2 kind.Though the amount in the nitride phosphor of this type of different elements is not particularly limited, with respect to general formula L XM YN ((2/3) X+ (4/3) Y): R or L XM YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): the fluor that R is represented, then 1000ppm is following is preferred.Because, promptly can obtain the cause of the fabulous characteristics of luminescence by taking below the 1000ppm.In order to obtain better luminous efficiency, amount that more preferably should the difference element is the scope that is set in 0.1～500ppm.
In the fluor after manufacturing, for the addition that makes different elements is the scope of 0.1～500ppm, the amount of dispersing of considering the different elements in the firing process being arranged also, is the above situation of 500ppm and make the addition of the different elements in the manufacturing processed.For example, also have in the firing process of manufacturing process, the amount of the different elements that will be added on raw material because of dispersing of different elements is also can the achieve the goal when above situation of performance of 10000ppm.Even but in this case, be adjusted to below the 10000ppm to preferred making in the thing amount of different elements at last, can reach the adjustment of the characteristics of luminescence of brightness etc. thus.
During L such as above-mentioned, by forming more than at least a kind among Mg, Ca, Sr, Ba, the Zn.Also promptly, L of the present invention also can be a kind element, and as L also can contain 2 go up with element.
For example, the mixture of Sr and Ca can change proportioning according to expectation.
During this situation, when Sr only being arranged or only Ca is arranged and Sr and Ca are mixed, then the peak wavelength of luminescent spectrum more is shifted in long wavelength side.The mol ratio of Sr and Ca roughly 5.5 o'clock, peak wavelength are shifted in long wavelength side, and the mol ratio of Sr and Ca 7: 3 or 3: 7 o'clock is compared to when only using Ca, Sr, and its peak wavelength is shifted in long wavelength side respectively.
M have the middle Si that is selected from C, Si, Ge be in the necessary IV family element more than at least a kind.Also promptly, present embodiment 1 can only be used Si as M, also can use combination, Si and the Ge of C and Si combination, C, Si, Ge combination in combination arbitrarily.
So, present embodiment 1 is necessary composition by Si in the composition of nitride phosphor, can obtain the fabulous nitride phosphor of crystallinity.
As example more specifically, can enumerate as using the Si of 95 weight %, and use the Ge of 5 weight %.
R have the Eu that is selected among Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, the Lu be in the necessary rare earth element more than at least a kind.Also promptly, in present embodiment 1, R can only be made up of Eu, also can be for containing Eu, and then contain the above-mentioned element of enumerating (element beyond the Eu) in the element more than 1 or 2.So, embodiment 1 can provide the nitride phosphor of excellent in luminous characteristics by the element that will use as R and fixed measure.
The embodiment that relates to embodiment 1 described later, it uses the europium (Eu) of rare earth element as luminescence center.Europium mainly has the accurate position of energy of divalent and 3 valencys.The fluor of present embodiment 1 is with respect to the alkaline-earth metal silicon nitride of parent, with Eu 2+Use as activator.In addition, present embodiment 1 and then by Eu and other activator, for example auxiliary activation such as Ce, Nd can and can be carried out the adjustment of luminous efficiency so that tone changes.
In present embodiment 1, the effect when adding the element different with above-mentioned L, above-mentioned M, above-mentioned O, above-mentioned N, above-mentioned R has as above-mentioned and can promote Eu 2+Diffusion and reach the advantage of raising of the characteristics of luminescence of tone, luminosity, twilight sunset etc.In addition, owing to can increase the particle diameter of fluorophor particle, so can reach the raising of brightness.And then Cr, Ni etc. have the effect that can shorten twilight sunset.Above-mentioned different elements can contain when making fluor and in the employed raw material, also can contain with the state of monomer or compound in manufacturing process, and can burn till together with raw material.But above-mentioned different elements also have the situation in the nitride phosphor that does not contain after burning till.Also have, even contain, nitrogen is compared to originally the only situation of residual less amount of addition (amount of adding) in raw material or manufacturing process.This is to be regarded as in firing process, the cause of dispersing because of above-mentioned different elements.
The fluor of present embodiment 1, absorb according to luminous element 10 and luminous ultraviolet to the part of blue light, and carry out the light in yellow to red zone luminous.For example the fluor of this embodiment 1 is used when the light-emitting device of Class1, by according to luminous element 10 and the colour mixture of the red colour system of luminous blueness system (not carrying out the light of wavelength conversion according to fluor) and fluor promptly can constitute the white color system light-emitting device that warm colour is.
In addition, in light-emitting device of the present invention, except the nitride phosphor of embodiment 1, also can have 1 light of going up the 1st luminescent spectrum of exporting so that self-emission device will be had, and at least a portion that absorbs light with the 2nd luminescent spectrum of exporting from the nitride phosphor of embodiment 1, and has the light different (from blue region to green area with the light wavelength that has absorbed, yellow area, till the red area) the fluor of the 3rd spectrographic light output of the peak wavelength more than at least 1, thus, promptly illuminant colour can be made multicolor.When so constituting, as fluor, containing at least with cerium activated yttrium with the 3rd luminescent spectrum. aluminum oxide is fluor, at least with cerium activated yttrium. gadolinium. aluminum oxide is a fluor and at least with cerium activated yttrium. gallium. aluminum oxide is that any at least of fluor serves as preferred more than 1.By containing above-mentioned yttrium. aluminum oxide is a fluor etc., promptly can be adjusted to the colourity of expectation easily.Particularly, can use Ln 3M 5O 12: R (Ln be selected among Y, Gd, the La more than at least 1.M contains at least any one party among Al, the Ga.R is a lanthanon), (Y 1-xGa x) 3(Al 1-yGa y) 5O 12: R for (R be selected among Ce, Tb, Pr, Sm, Eu, Dy, the Ho more than at least 1.0＜R＜0.5)。This type of fluor is from the light of the wavelength domain of the short wavelength side of near ultraviolet visible light, 270～500nm and be excited, and has the peak wavelength of luminescent spectrum at 500～600nm.But in the present invention, the fluor with the 3rd luminescent spectrum is not limited to above-mentioned fluor, can use various fluor.
The activated yttrium with cerium. aluminum oxide is a fluor etc., absorbs according to luminous element 10 and the part of luminous blueness system and carry out the light of yellow area luminous.Herein, by according to luminous element 10 and luminous blueness system and yttrium. aluminum oxide is the light of colour mixture of the sodium yellow of fluor, becomes blue white white.Therefore, according to this yttrium. aluminum oxide is that fluor and above-mentioned nitride phosphor are mixed together the measure of using with the coating member with light transmission, promptly can basis and the combination of luminous blueness system constitutes warm colour or bulb look by luminous element 10 white color system light-emitting device.In addition, the combination by suitably changing fluor or the amount of each fluor promptly can provide the white color system light-emitting device with various spectral distribution.Also have, increase warm colour or red white color system light-emitting device, be meant that it is 75 to 95 that several Ra are commented in average colour developing, colour temperature is 2000 to 8000K.Also can be with white, color of sunshine of the bulb look of realizing the JISZ9112 specification, temperature white, white, daytime.In light-emitting device of the present invention, particularly preferably being average colour developing, to estimate number Ra and colour temperature be the white color system light-emitting device that is positioned on the track of blackbody radiation of chromaticity diagram.Wherein, because the colour temperature of expectation and the light-emitting device that number is estimated in average colour developing are provided, so can certainly be suitably to change yttrium. aluminum oxide is the use level of fluor and fluor of the present invention.The white color system light-emitting device of this warm colour system more can reach the improvement that number R9 is estimated in special colour developing.Blue based light-emitting device in the past and with cerium activated yttrium. the white color system light-emitting device of the combination of aluminum oxide fluor, special colour developing estimate number R9 for roughly closely 0, and red composition is inadequate.Therefore, improve special colour developing evaluation number R9 and become the solution problem, but by fluor of the present invention is contained at yttrium. in the aluminum oxide fluor, promptly special colour developing can be estimated number R9 and be increased to till 60 to 70.Herein, special colour developing is estimated number R9 trying to achieve for each color shift of other colour code of 7 kinds with average color developing, and be not 7 kinds on average.It is representative with the skin (Japanese) green, the people than the red, yellow, green, blue of higher chroma, people's skin (white man), leaf certainly that 7 kinds colour code is selected.Be called R9, R respectively successively and be 10, R is 11, R is 12, R is 13, R is 14, R is 15.Wherein, R9 represents red colour code.
In addition, the fluor that uses with nitride phosphor combination of the present invention is not limited to yttrium. and aluminum oxide is a fluor etc., can reach and yttrium. aluminum oxide is the identical purpose of fluor, from blue region till green area, yellow area, the red area, the fluor that possesses the 3rd luminescent spectrum of the peak wavelength that has more than 1 also can be to use with above-mentioned nitride phosphor combination.Thus, promptly can provide white color system light-emitting device according to the colour mixture principle of light.As the concrete thing of the fluor that uses with the nitride phosphor combination, green is light-emitting fluophor SrAl 2O 4: Eu, Y 2SiO 5: Ce, Tb, MgAl 11O 19: Ce, Tb, Sr 7Al 12O 25: Eu, (Mg, Ca, Sr, Ba in more than at least 1) Ga 2S 4: Eu, blueness are light-emitting fluophor Sr 5(PO 4) 3Cl: Eu, (SrCaBa) 5(PO 4) 3Cl: Eu, (BaCa) 5(PO 4) 3Cl: Eu, (Mg, Ca, Sr, Ba in more than at least 1) 2B 5O 9Cl: Eu, Mn, (Mg, Ca, Sr, Ba in more than at least 1) (PO 4) 6Cl 2: Eu, Mn, red colour system light-emitting fluophor Y 2O 2S: Eu, La 2O 2S: Eu, Y 2O 3: Eu, Gd 2O 2S: Eu etc., this is formed according to change, i.e. the luminescent spectrum that can obtain to expect.Wherein, the light-emitting fluophor of green, blueness, redness etc. is not limited to above-mentioned fluor, can use various fluor.
(manufacture method of the fluor of embodiment 1)
Then, use Fig. 4 and contain the Ca of B with manufacturing 2Si 5N 8: the Eu situation illustrates the manufacture method of the fluor of embodiments of the present invention 2 for example.
Also have, the present invention is not limited to this manufacture method.In addition, fluor contains Li, Na, K, B etc. and O.
(1) operation P1.
This manufacture method is at first pulverized (P1 of Fig. 4) with the Ca of raw material.
Ca use Ca monomer as raw material is preferred, but also can use the compound of imide compound, amide compound etc.In addition, raw materials of Ca also can contain Li, Na, K, B, Al etc.Raw material is that purified is preferred.Thus, owing to do not need refining step, thus can simplify the manufacturing process of fluor, and cheap nitride phosphor can be provided.As the target of the pulverizing of Ca, the following scope of the above 15 μ m of the about 0.1 μ m of median size, and from the reactivity of other raw material, when burning till and the viewpoint of the particle diameter control of burning till etc. for preferably, but the present invention is not limited to this scope.The purity 2N of Ca is above to be preferred, but is not limited to this.
(2) operation P2.
In nitrogen atmosphere, the Ca of the raw material pulverized is carried out nitrogenize (P2).
This reaction formula is with formula 1 expression.
(formula 1)
In nitrogen atmosphere, with 600～900 ℃ temperature raw materials of Ca was carried out nitrogenize about 5 hours, can obtain the nitride (Ca of Ca 3N 2).The nitride of Ca is highly purified to be preferred.
(3) operation P3.
Nitride (Ca with Ca 3N 2) pulverize.
(4) operation P4.
Operation P4 pulverizes the Si of raw material.
It is preferred that the Si of raw material uses monomer, but also can use nitride-based compound, imide compound, amide compound etc.Si for example 3N 4, Si (NH 2) 2, Mg 2Si etc.The purity 3N of the Si of raw material is above to be preferred, but also can contain Li, Na, K, B; The different elements of Al, Cu etc.The median size of the Si compound after the pulverizing is the scope below the 15 μ m more than about 0.1 μ m, from the reactivity of other raw material, the viewpoint of particle diameter control etc. when burning till and after burning till for preferably.
(5) operation P5.
In nitrogen atmosphere, the Si of the raw material pulverized is carried out nitrogenize.
This reaction formula is shown in formula 2.
(formula 2)
The silicon Si of this pulverizing also in nitrogen atmosphere, carried out nitrogenize about 5 hours with 800～1200 ℃ temperature, obtained silicon nitride therefrom.Nitrogenize used in the present invention is that silicon is highly purified for preferred.
(6) operation P6.
Operation 6 is pulverized the nitride of Si.
(7) operation P7.
Among the operation P7 with the compound H of B 3BO 3Wet mixing is at the compd E u of Eu 2O 3(P7).Compound as Eu uses europium sesquioxide, but also can use metal europium, nitrogenize europium etc.In addition, the Eu of raw material also can use imide compound, amide compound.Europium sesquioxide is highly purified to be preferred.Different elements with the compound of B etc. carry out wet mixing herein, mix but also can carry out dry type.
Be the influence of sneaking into when crucible, stove material constitute in element or the raw material in order to estimate element-specific herein, and with each element (different element) easily the state of diffusion diffusion add in the nitride.Also promptly, it is equal that the salt of each element that this place adds can be estimated as the common form, elemental metals or the oxide compound that have with crucible, stove material, or its above elemental diffusion.
This manufacture method is that example illustrates when adding B, so use the compound H of B 3BO 3, but the present invention has Li, Na, K etc. as the different elements beyond the B, as this type of compound, for example can use H 2MO 4, LiOH.H 2O, Na 2CO 3, K 2CO 3, RbCl, CsCL, Mg (NO 3) 2, CaCl 2.6H 2O, SrCl 2.6HO, BaCl 2.2H 2O, TiOSO 4.H 2O, ZrO (NO 3) 2, HfCl 4, VCl 3, Nb 2O 5, TaCl 5, Cr (NO 3) 3.9H 2O, H 2WO 4, ReCl 5, FeCl 3.3H 2O, RuCl 3.2H 2O, Co (NO 3) 3.6H 2O, NiCl 2.H 2O, IrCl 3, PdCl 2, H 2PtCl 6.6H 2O, Cu (CH 3COO) 2.H 2O, AgNO 3, HAuCl 4.4H 2O, Zn (NO 3) 2.6H 2O, H 3BO 3, Al (NO 3) 3.9H 2O, GaCl 3, InCl 3, GeO 2, Sn (CH 3COO) 2, Pb (NO 3) 2, (NH 4) 2HPO 4, Sb 2O 3, Bi (NO 3) 3.5H 2O, (NH 4) 2SO 4Deng.In addition, be that example illustrates so that this compounds is added the nitride of Si, the compound of Eu etc. in addition, but also can in the raw material of the nitride of Ca, the nitride of Si, the compound of Eu etc. is formed, contain different elements.
(8) operation P8.
Operation P8 is in oxidizing atmosphere, with the compd E u of Eu 2O 3With compound H 3BO 3Mixture burn till.
(9) operation P9.
Operation P9 pulverizes the mixture of Eu and B.
The median size of Eu after the pulverizing and the mixture of B, about 0.1 μ m to 15 μ m is preferred.
(10) operation P10.
The mixture of the nitride of Ca after operation 10 will be pulverized, nitride, Eu and the B of Si mixes.
(11) operation P11.
Operation 11 is burnt till the mixture of nitride, Eu and the B of the nitride of Ca, Si in ammonia atmosphere.Burn till processing to be added with the Ca of B by this 2Si 5N 8: Eu and the fluor represented.The reaction formula of the nitride phosphor that will produce according to burning till of operation 11 is shown in the formula 3.
(formula 3)
Make the fluor of embodiment 1 as above processing.
Firing temperature can burn till 1200 to 2000 ℃ scope, but 1400 to 1800 ℃ firing temperature is preferred.Burn till is with heating up lentamente and carrying out stage that a few hours burn till at 1200 to 1500 ℃ and burn till to preferably, carry out burning till of fs but also can use at 800 to 1000 ℃, and heating and carry out the two-stage that subordinate phase burns till at 1200 to 1500 ℃ and burn till (multistage burns till) lentamente.The raw material of fluor uses boron nitride (BN) material crucible, boat and burns till to preferably.Outside the crucible of boron nitride material, also can use aluminum oxide (Al 2O 3) the material crucible.This type of B, Al etc. more can reach the raising of brightness than Mo, and the fluor with high-luminous-efficiency can be provided.
In addition, reducing atmosphere is the atmosphere more than at least a kind that contains nitrogen, hydrogen, argon, carbonic acid gas, carbon monoxide, ammonia.But, under the reducing atmosphere beyond this type of, also can be to burn till.
In the manufacture method of above explanation,, promptly can change composition as the fluor of purpose by changing each raw material and cooperating ratio.
By using above manufacture method, promptly can obtain fluor as purpose.
(luminous element)
In the present invention, luminous element has the spectrographic semiconductor light-emitting elements of excited fluophor effectively (also promptly, having the semiconductor light-emitting elements that the light of the luminescent spectrum of excited fluophor effectively carries out luminous luminescent layer) for preferred.As the material of such semiconductor light-emitting elements, can enumerate as various semi-conductors such as BN, SiC, ZnSe or GaN, InGaN, InAlGaN, AlGaN, BalGaN, BinAlGaN.The luminescence center that also can contain in addition, Si or Zn etc. as impurity element at this type of element.The ultraviolet region of excited fluophor is to visible light effectively, as the material that can effectively the light in short wavelength territory be carried out luminous luminescent layer, particularly enumerate nitride semiconductor (for example, as the nitride-based semiconductor that contains Al or Ga, contain the nitride-based semiconductor of In or Ga, In XAl YGa 1-X-YN, 0＜X＜1,0＜Y＜1, X+Y1) more suitable.
In addition, as semiconductor structure, can enumerate have that MIS engages, PIN engages or homogeneous texture, heterojunction structure or double-heterostructure that pn engages etc. for suitably.According to the material of semiconductor layer or its mixed crystal than carrying out the various selections of emission wavelength.In addition, by being formed on single quantum well structure or the multiple quantum trap structure that the semiconductor active layer is produced the film of quantum effect, also can improve output.
When using nitride-based semiconductor, the material that substrate uses sapphire, spinel, SiC, Si, ZnO, GaAs, GaN etc. is for well.For productivity forms crystallinity nitride-based semiconductor preferably excellently, it is preferred utilizing sapphire substrate.On this sapphire substrate, can use HVPE method or mocvd method etc. and the formation nitride-based semiconductor.During this situation, shape makes the buffer layer of the on-monocrystalline of growth such as GaN, AlN, GaAIN with low temperature on sapphire substrate, and forms the nitride-based semiconductor with pn joint thereon.
The making that can effectively the ultraviolet region with the pn joint that uses this nitride-based semiconductor be carried out luminous luminous element is for example following.
At first, on buffer layer and the shiny surface of sapphire substrate slightly vertically with SiO 2Form striated.Use the HVPE method thereon and make GaN carry out ELOG (Epitaxial LateRal OveR is that GR is ows Gan) growth.Then, stack gradually by the 1st contact layer of being formed by n type gan, by n type aluminium nitride according to mocvd method. the 1st coating that gallium is formed, stacked a plurality of indium nitrides. aluminium. the trap layer and the aluminium of gallium. the active coating of the multiple quantum trap structure of the barrier layer of gallium, by p type aluminium nitride. the 2nd coating that gallium is formed, formed the 2nd contact layer by p type gan.
In addition, also can not use ELOG to grow up and as following.
The GaN of intermediary buffer layer and on sapphire substrate 1 for example stacks gradually the N type contact layer formed by the n type GaN layer of the Si that do not mix, by the n type GaN that is doped with Si, not the p coating formed of the luminescent layer of Doped GaN layer, multiple quantum trap structure (quantum well structure of GaN battle array parietal layer/InGaN trap layer), the p type GaN that is made up of the p type GaN of doped with Mg and the p type contact layer be made up of the p type GaN of doped with Mg.Then, following and form electrode.
The P resistance electrode is formed on roughly comprehensive on the p type contact layer, and the part on this p resistance electrode is formed with p connection gasket plate electrode 3.
In addition, the n electrode is removed not Doped GaN layer from p type contact layer, and is exposed the part of n type contact layer, and be formed on the part that this exposes according to etching mode.
Also have, though present embodiment is used the luminescent layer of multiple quantum trap structure, the present invention is not limited thereto, and for example can make the single quantum well structure that utilizes InGaN, also can utilize the n type that is doped with Si, Zn etc., the GaN of p type impurity.
In addition, the luminescent layer of luminous element 10 changes by the amount that makes In, and in the scope of 420nm to 490nm, can change the main light emission peak value.In addition, emission wavelength is not limited to above-mentioned scope, can use the person that has the emission wavelength at 360～550nm.
So handle, promptly can on substrate, constitute the semiconductor light-emitting elements of double-heterostructure.In addition, the present invention also can use active coating is made the ridge shape and the syntonizer end face of holding under the arm with guide layer is set and the semiconductor Laser device that constitutes.
Nitride-based semiconductor is represented the n type electroconductibility under the not doping state.But, for improve luminous efficiency with the carrier concn of each layer be set in decide in the scope for preferred, but for the n type nitride-based semiconductor of the expectation that forms management carrier concentration, it serves as preferred then mixing suitably to import Si, Ge, Se, Te, C etc. as the n type.On the other hand, when forming p type nitride-based semiconductor, the Zn of doped p type doping agent, Mg, Be, Ca, Sr, Ba etc. are preferred.Nitride-based semiconductor is difficult to make the p typeization owing to doped p type only mixes, thus the p type mix import after, reach low resistance according to the processing of the heating of stove or plasma irradiation etc. and turn to preferably.Make when not removing the structure of sapphire substrate, partially till p type side is etched to the surface of the 1st contact layer, and exposing the contact layer of p side and n side, and forming electrode respectively on each contact layer with the one side side.Then, make the luminous element of forming by nitride-based semiconductor by the measure that cuts into shaped like chips.
In light-emitting device, luminous element is because illuminant colour in order to realize being required, though selected in the Central Shanxi Plain of the emission wavelength of the fluor that has used and excitation wavelength, this moment, also cooperate the light of considering because of translucent resin to produce factors such as deterioration, and suitably select.The present invention also can use at ultraviolet region has luminescent spectrum, and its main light emission wavelength is below the above 420nm of 360nm, or the following person of the above 470nm of 450nm.
Herein, in semiconductor light-emitting elements, with impurity concentration 10 17～10 20/ cm 3And the sheet resistance R of the n type contact layer that forms be the sheet resistance R of n and electrode is p, with can become R be p 〉=R be n the pass state and be adjusted to preferred.Particularly, n type contact layer more preferably then is 4～6 μ m owing to be formed on for example thickness 3～10um, is estimated 10～15 Ω/ so this sheet resistance R is n.Therefore, Ci Shi R is p can have above-mentioned thin-film electro resistance (the thin-film electro resistance that 10～15 Ω/) are above and be formed on film and get final product.In addition, light transmission p electrode thickness is that the following film of 150 μ m forms also passable.In addition, the p electrode also can use metal ITO, ZnO in addition.Also can make the electrode that a plurality of light that possess mesh electrode etc. take out with peristomes herein and form, to replace light transmission p electrode.
In addition, multilayer film that light transmission p electrode is formed with other element of a kind in the gold and the group of platinum group metal element and a kind at least or alloy and when forming, adjust the sheet resistance of light transmission p electrode according to the amount of already contg gold or platinum group metal element, improve stability and reproducibility therefrom.Gold or metallic element be owing to use absorption number in the wavelength region may of semiconductor light-emitting elements of the present invention for higher, and perviousness better so the amount at the gold of light transmission p electrode or platinum group metal element of containing heals at least.Because the pass of in the past semiconductor light-emitting elements sheet resistance is that p 〉=R is n for R, and R of the present invention be p 〉=R is n, so light transmission p electrode is compared in the past the person and more can forms film.This filming is easy to realize reducing the amount of gold or platinum group metal element.
As above-mentioned, semiconductor light-emitting elements used in the present invention, the sheet resistance R of n type contact layer are that the sheet resistance R of n Ω/ and light transmission p electrode be p Ω/ for forming R is that p 〉=R is that the pass of n is for preferred.But after making semiconductor light-emitting elements, being difficult to measure R is n, and can not learn the relation of Rp and Rn in fact, still, and the state of light intensity distributions that can be when luminous and learn that R how is that p and R are the pass of n.
In addition, in luminous element, light transmission p electrode and n type contact layer are that to have R be p 〉=R when being the pass of n, be connected above-mentioned light transmission p electrode and be provided with have prolong conducting part p side dado electrode for preferred, more can reach the raising of external quantum efficiency therefrom.Prolong the shape and the direction and unrestricted of conducting part, and when prolonging conducting part and being linearity, be preferably owing to can reduce the shading area, but also can be for netted.In addition, at vpg connection, except linearity, also can be curve-like, reticulation, dendritic, hook-shaped.At this moment, owing to the total area that is directly proportional in p side dado electrode increases shaded effect,, shaded effect designs wire spoke and the length that prolongs conductive part so can not improving the state of luminous reinforced effects.
(coating member)
Coating member 12 (light translucent material) is arranged in the cup of lead frame 13, and and the fluor 11 that conversion is carried out in luminous element 10 luminous mixed and uses.As the concrete material of coating member 12, can use the temperature profile of Resins, epoxy, urea-formaldehyde resin, silicone resin etc., the transparent resin that has excellent weather resistance, silicon sol, glass, inorganic binder etc.In addition, also can all contain diffusant, barium titanate, titanium oxide, aluminum oxide etc. with fluor 11.In addition, also can contain Photostabilised dose or tinting material.
(lead frame)
Lead frame 13 constitutes by lead-in wire 13a and inner lead-in wire 13b are installed.
Lead-in wire 13 is installed is used in configuration luminous element 10.Cup-shaped is formed at the top that lead-in wire 13a is installed, and luminous element 10 is bonded in this cup.Then, cover the outside surface of this luminous element 10 with the coating member 12 that contains fluor 11 at cup.Also can dispose a plurality of luminous elements 10 in cup, and lead-in wire 13a will be installed utilize as the common electrode of a plurality of luminous elements 10.At this moment, be required the connectivity of sufficient electrical conductivity and conducting wire 14.Luminous element 10 and the cup that lead-in wire 13a is installed engage (following), can be undertaken by heat-curing resin etc.Can enumerate as Resins, epoxy, acrylic resin, imide resin etc. as heat-curing resin.In addition,, luminous element is bonded on anchor leg 13a and is electrically connected, can use Ag paste, carbon paste agent, metal coupling etc. by (face down configuration) such as flip-chip bonding pads.In addition, also can use inorganic binder.
In addition, inner lead 13b is electrically connected according to being configured in electrode 3 and conducting wire 14 that the luminous element 10 on the lead-in wire 13a is installed.Inner lead 13b for fear of with electrically contacting of lead-in wire 13a is installed, leave the position that lead-in wire 13a is installed and be configured in.When a plurality of luminous element 10 is set on lead-in wire 13a is installed, must make each conducting wire between can discontiguous state and the formation that disposes.Inner lead 13b uses and the identical material of lead-in wire 13a is installed for preferred, can use iron, copper, the copper of the iron of packing into, gold, white gold and silver etc.
(conducting wire)
Conducting wire 14 is electrically connected the electrode 3 and the lead frame 13 of luminous element 10.Conducting wire 14 and the good person of electrode 3 resistives, mechanical connection, electrical conductivity and heat conductivity are preferred.As the metal of the concrete material gold of conducting wire 14, copper, platinum, aluminium etc. and this type of alloy etc. is preferred.
(modular unit)
Modular unit 15 is in order to be provided with from outer protection luminous element 10, fluor 11, coating member 12, lead frame 13 and conducting wire 14 etc.Modular unit 15 is from outside the protection purpose of outside, also has the expanded field of vision angle, relaxes the directive property of self-emission device, with the luminous purpose of bringing together and spreading.In order to reach this type of purpose, modular unit is formed on the shape of expectation.Also promptly, modular unit 15 also can cooperate purpose and outside convex lens shape, concavees lens shape, make a plurality of stacked structures.Concrete material as model assembly 15 can use Resins, epoxy, urea-formaldehyde resin, advises resin, the material of the light transmission of silicon sol, glass etc., weathering resistance, excellent in temperature characteristic.This model assembly 15 also can contain diffusant, tinting material, UV light absorber or fluor.As diffusant barium titanate, titanium oxide, aluminum oxide etc. is preferred.Because and the repellency of the material of coating member 12 is less, so then use identical material for preferred when considering specific refractory power.
Embodiment 2
The light-emitting device of embodiment 2 is identical with embodiment 1, has at least:
Luminous element, it has the 1st luminescent spectrum; And
Fluor, its at least a portion with above-mentioned the 1st luminescent spectrum is carried out wavelength conversion, and has the 2nd luminescent spectrum.
The light-emitting device of present embodiment 2 for example only uses nitride phosphor described later as fluor 11.Fluor 11 absorb by luminous element 10 and luminous ultraviolet to the part of the light of blue region, and carry out the light in yellow to red zone luminous.The light-emitting device that the light-emitting device of embodiment 2 uses this fluor 11 at Class1, and according to by luminous element 10 and the colour mixture of the red colour system of luminous blueness system and fluor, and the white or the peach soft color and taste that are with warm colour carry out luminous light-emitting device.The light-emitting device of embodiment 2 is according to the colour mixture of the red colour system of blue light, fluor, yellow-green light that YAG is fluor, and can carry out the luminous light-emitting device of the bulb look of JIS specification.
Herein, the bulb look is meant that with the point on the track of the blackbody radiation of white color system 2500～3500K degree of JIS specification (JIS Z8110) be the scope of center made.Also be provided at the light-emitting device that (light) yellow (orange) is pink, pink, (light) is pink, (yellowing) white zone has illuminant colour of the tristimulus coordinates of Fig. 8 as other color and taste.
Also have, the light-emitting device of embodiment 2 is not limited to form 1, and for example Type II also can.
Below, the fluor that relates to present embodiment 2 is described.
The fluor of present embodiment 2 contains: according to the II family element more than at least a kind in the group of being made up of Be, Mg, Ca, Sr, Ba, Zn of being selected from that is selected from that the rare earth element more than at least a kind in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Lu is activated; IV family element more than at least a in the group that C, Si, Ge, Sn, Ti, ZR, Hf formed; And the nitride phosphor of N, and then contain the following B of the above 10000ppm of 1ppm.In addition, also can contain O (oxygen) in the composition of this nitride phosphor.In the various amide fluor of above-mentioned combination, the Ca that is activated according to Eu and any at least 1 nitrogenize fluor that element, Si and N formed of Sr are that nitride phosphor below the above 10000ppm of 1ppm serves as preferred to contain B.The part of Eu can be according to being selected from of being selected from that the rare earth element more than at least a kind in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Lu is activated by the II family element of selecting in Be, Mg, Ca, Sr, Ba, the group formed more than at least a kind; The IV family element more than at least a kind in the group that C, Si, Ge, Sn, Ti, ZR, Hf formed; And the nitride phosphor of N, and then B contains below the above 10000ppm of 1ppm.In addition, also can contain O in the composition of this nitride phosphor.In the various ammonification fluor of above-mentioned combination, the Ca that is activated according to Eu and any at least 1 nitrogenize fluor that element, Si and N formed of Sr are that nitride phosphor below the above 10000ppm of 1ppm serves as preferred to contain B.The part of Eu can be replaced according to the rare earth element more than a kind that is selected from the group of being made up of Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Lu at least.The part of the element of at least any one party of Ca and Sr, the II family element more than at least a kind in the group that optional free Be, Mg, Ca, Sr, Ba, Zn formed and replacing.The part of Si can be replaced by being selected from the IV family element more than a kind in the group of being made up of C, Ge, Sn, Ti, ZR, Hf at least.
Also promptly, the luminous fluor of present embodiment 2 is with general formula L XM YN ((2/3X)+(4/3Y): R system or L XM YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): (L is selected from the II family element more than at least a kind in the group of being made up of Be, Mg, Ca, Sr, Ba, Zn in R system.M is selected from the IV family element more than at least a kind in the group of being made up of C, Si, Ge, Sn, Ti, ZR, Hf.R system is selected from the rare earth element more than at least a kind in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Lu.X, Y, Z0.5≤X≤3,1.5≤Y≤8,0＜Z≤3) represented nitride phosphor, B contains below the above 10000ppm of 1ppm.Enumerate as (Sr as the concrete example that contains at general formula TCa 1-T) 2Si 5N 8: Eu, Ca 2Si 5N 8: Eu, Sr TCa 1-TSi 7N 10: Eu, SrSi 7N 10: Eu, CaSi 7N 10: Eu, Sr 2Si 5N 8: Eu, Ba 2Si 5N 8: Eu, Mg 2Si 5N 8: Eu, Zn 2Si 5N 8: Eu, SrSi 7N 10: Eu, BaSi 7N 10: Eu, MgSi 7N 10: Eu, Zn Si 7N 10: Eu, Sr 2Ge 5N 8: Eu, Ba 2Ge 5N 8: Eu, Mg 2Ge 5N 8: Eu, Zn 2Ge 5N 8: Eu, SrGe 7N 10: Eu, BaGe 7N 10: Eu, MgGe 7N 10: Eu, ZnGe 7N 10: Eu, Sr 1.8Ca 0.2Si 5N 8: Eu, Ba 1.8Ca 0.2Si 5N 8: Eu, Mg 1.8Ca 0.2Si 5N 8: Eu, Zn 1.8Ca 0.2Si 5N 8: Eu, Sr 0.8Ca 0.2Si 7N 10: Eu, Ba 0.8Ca 0.2Si 7N 10: Eu, Mg 0.8Ca 0.2Si 7N 10: Eu, Zn 0.8Ca 0.2Si7N 10: Eu, Sr 0.8Ca 0.2Ge 7N 10: Eu, Ba 0.8Ca 0.2Ge 7N 10: Eu, Mg 0.8Ca 0.2Ge 7N 10: Eu, Zn 0.8Ca 0.2Ge 7N 10: Eu, Sr 0.8Ca 0.2Si 6GeN 10: Eu, Ba 0.8Ca 0.2Si 6GeN 10: Eu, Mg 0.8Ca 0.2Si 6GeN 10: Eu, Zn 0.8Ca 0.2Si 6GeN 10: Eu, Sr 2Si 5N 8: Pr, Ba 2Si 5N 8: Pr, Sr 2Si 5N 8: Tb, BaGe 7N 10: Ce (0＜T＜1).
B passes through to add boron compound at various raw materials, and mixes and can add easily with wet type or dry type.In addition, also can contain boron (B) in advance at Ca 3N 2, Si 3N 4Deng raw material.For example, carry out wet mixing and add H 3BO 3The time, the above 1000ppm of 1ppm is following to be preferred.Particularly the above 1000ppm of 100ppm is following is preferred.Carry out that dry type is mixed and when adding boron, be preferred below the above 10000ppm of 1ppm.Particularly the above 10000ppm of 100ppm is following is preferred.This boron works as fusing assistant.The boron that is added on raw material can use boron, boride, boron nitride, boron oxide, borate etc.Particularly can enumerate as BN, H 3BO 3, B 2O 6, B 2O 3, BCl 3, SiB 6, CaB 6Deng.This type of boron compound is added on raw material with the quantitative weighing of institute.Toward the addition of the boron of raw material with burn till after the amount of boron differ be decided to be consistent.Because boron partly disperses in that burning till in the stage of manufacturing process is existing, thus the amount of the boron after burning till, during toward the interpolation of raw material still less.
L is selected from the II family element more than at least a kind in the group of being made up of Be, Mg, Ca, Sr, Ba, Zn.Therefore, also can use Mg, Ca, Sr etc. separately, but also can be used as the combination of Ca and Sr, Ca and Mg, Ca and Ba, Ca and Sr and Ba etc.Particularly pass through to use the composition of at least any one party of Ca and Sr, promptly can provide excellent fluor such as luminosity, quantum yield at nitride phosphor.Element with at least any one party of this Ca and Sr, and a part of replacing Ca and Sr with Be, Mg, Ba, Zn.When using the mixture more than 2 kinds, can change proportioning according to expectation.Herein, when Sr only being arranged or only Ca is arranged, and Sr and Ca mixing aspect peak wavelength are for more being shifted in long wavelength side.The mol ratio of Sr and Ca 7: 3 or 3: 7 o'clock is compared to when only using Ca, Sr, and peak wavelength is shifted in long wavelength side.And then the mol ratio of Sr and Ca roughly 5: 5 o'clock, then peak wavelength is shifted in long wavelength side.
M is selected from the IV family element more than at least a kind in the group of being made up of C, Si, Ge, Sn, Ti, ZR, Hf.Therefore, though can use C, Si, Ge etc. separately, also can make the combination of C and Si, Ge and Si, Ti and Si, ZR and Si, Ge and Ti and Si etc.Particularly, promptly can provide the nitride phosphor of cheapness and good crystallinity by Si being used composition at nitride phosphor.Also can be with the part of C, Ge, Sn, Ti, ZR, Hf replacement Si.When to use Si be necessary mixture, and change proportioning according to expectation.For example, can use the Si of 95 weight %, and use the Ge of 5 weight %.
R is selected from the rare earth element more than at least a kind in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Lu.Though also can use Eu, Pr, Ce etc. separately, also can make the combination of Ce and Eu, Pr and Eu, La and Eu etc.Particularly, promptly can be provided at the yellow nitride phosphor that has the excellent in luminous characteristics of peak wavelength to red area by use the measure of Eu as activator.Also can be with the part of Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Lu replacement Eu.By a part of replacing Eu with other element, then other element acts on as being activated.By the measure of taking to be activated, get final product so that tone changes, and can carry out the adjustment of the characteristics of luminescence.When to use Eu be necessary mixture, can change proportioning according to expectation.The embodiment that relates to embodiment 2 uses the europium Eu of rare earth element as luminescence center.Europium is mainly the accurate position of the energy with divalent and 3 valencys.Fluor of the present invention uses Eu with respect to the alkaline-earth metal silicon nitride of parent 2+And as activator.
Effect when adding boron can promote Eu 2+Diffusion, and reach the raising of sending out into the characteristics of luminescence of luminosity, energy efficiency, quantum yield etc.In addition, particle diameter can be increased, and the raising of the characteristics of luminescence can be reached.
Above-mentioned nitride phosphor so also can contain 1 above 500ppm following to be selected from by Li, Na, K, R be the I family element more than at least a kind in the group formed of b, Cs.I family element has been because dispersed when the burning till of manufacturing process, so be compared to toward the interpolation of raw material originally, the addition after then burning till becomes more a small amount of.Therefore, the amount of adding raw material is adjusted into below the 1000ppm to preferred.Thus, promptly can reach the adjustment of the luminous efficiency of luminosity etc.By adding I family element, promptly can as above state, reach the raising of luminosity, quantum yield.
Above-mentioned nitride phosphor so also can comprise 1 above 500ppm following by I family element that Cu, Ag, Au formed, the IV family element of being formed by iii group element that Al, Ga, In formed, by Ti, ZR Hf, Sn, Pb, V group element, the element more than at least a kind in the VI family element that S formed by P, Sb, Bi formed.This type of element also with I family element in the same manner because when the burning till of manufacturing process, this type of element disperses, so toward the interpolation of raw material originally, the addition aspect after then burning till becomes more a small amount of.Therefore, the amount that is added on raw material is adjusted into below the 10000ppm to preferred.By adding this type of element, promptly can carry out the adjustment of luminous efficiency.
Above-mentioned nitride phosphor and then also can contain the element arbitrarily of following Ni, Cr of 1 above 500ppm.Because it can regulate the cause of twilight sunset.Therefore, the amount that is added on raw material is adjusted into below the 1000ppm to preferred.
And then be added on the element of above-mentioned nitride phosphor, usually with oxide compound or oxidizing water oxide compound and add, but be not limited to this, also can be metal, nitride, imide, acid amides or other inorganic salts, in addition, also can make the state that contains in advance at other raw material.
Oxygen contains in the composition of above-mentioned nitride phosphor.Oxygen is to be considered to import from the various oxide compounds that constitute raw material, or sneaks into oxygen in burning till.This oxygen is considered to have and promotes Eu diffusion, the effect that grain is grown up, crystallinity improves.Also promptly, even will use a compound at raw material to change over metal, nitride, oxide compound, though also can obtain identical effect, it is bigger situation that the effect when using oxide compound is also arranged.The crystalline texture of nitride phosphor though oblique crystal or iris are arranged, also has the form of on-monocrystalline, big prismatic crystal etc.
The fluor of above embodiment 2 can basis be made with embodiment 1 identical method.
In addition, during this situation, the operation of P7～P9 is omitted, and in the operation of P10, also can be utilized dry type, the nitride of Ca, the nitride of Si, the compd E u of Eu 2O 3, B compound H 3BO 3Mix.
In addition, in the light-emitting device of embodiment 2, as employed fluor, except the nitride phosphor of above-mentioned embodiment 2, any at least fluor more than 1 of the fluor of blue-light-emitting, the fluor of green emitting, the yellow fluor that takes place can be mixed and uses.
Though blueness is luminous fluor, the fluor of green emitting, yellow is that luminous fluor has various fluor, particularly using at least with cerium activated yttrium. aluminum oxide is fluor, at least with cerium activated yttrium. gadolinium. aluminum oxide is a fluor and at least with cerium activated yttrium. gallium. aluminum oxide is that any at least of fluor serves as preferred more than 1.The light-emitting device of the illuminant colour with expectation promptly can be provided thus.Use the fluor of present embodiment 2 and with cerium activated yttrium. when aluminum oxide is a fluor etc., because absorbing of this type of fluor itself is less, so can take out luminous effectively.Particularly, can use Ln 3M 5O 12: R system (Ln in Y, Gd, La more than at least 1.M contains at least any one party of Al, Ga.R is a group of the lanthanides), (Y 1-xGax) 3(Al 1-yGa y) 5O 12: R (R be selected among Ce, Tb, Pr, Sm, Eu, Dy, the Ho more than at least 1.0＜R system＜0.5).This fluor is excited by the light of the wavelength domain of the short wavelength side of visible light, 270～500nm near ultraviolet, and has peak wavelength at 500～600nm.Wherein, have the fluor of the 3rd luminescent spectrum of this blueness etc., be not limited to above-mentioned fluor, can use various fluor.
As the excitation light source of the fluor of present embodiment 2, semiconductor light-emitting elements, laser diode, the ultraviolet radiation that is produced, the ultraviolet radiation that is produced etc. are arranged in the sunlight post of glow discharge in the sunlight post of arc-over.But using the semiconductor light-emitting elements of light of radiation near ultraviolet region and laser diode, blueness as excitation light source is that the luminous semiconductor light-emitting elements of luminous semiconductor light-emitting elements and laser diode and blue-greenish colour and laser diode are for preferred.
Also have the light from the short wavelength zone of near ultraviolet visible light, near the wavelength region may till being meant the 270nm to 500nm.
Embodiment 3
The light-emitting device of embodiments of the present invention 3 is light-emitting devices of form 1 (bullet cut) shown in Figure 1, except use fluor described later, identical with embodiment 1 and constitute.
Below, be described in detail the fluor that relates to light-emitting device of the present invention.
The fluor of embodiments of the present invention 3, with L-M-N: Eu, WR system or L-M-O-N: Eu, WR system (L contain be selected from the group of being formed by the II valency of Be, Mg, Ca, Sr, Ba, Zn more than at least a kind.M contain be selected from the group of being formed by the IV valency of C, Si, Ge, Sn, Ti, ZR, Hf more than at least a kind.N nitrogen.Eu is an europium.WR is the rare earth element except Eu) represented.
The following description relates in the fluor of embodiments of the present invention 3, mainly be Ca-Si-N: Eu, WR system or Sr-Si-N: Eu, WR system or Sr-Ca-Si-N: Eu, WR system or Ca-Si-O-N: Eu, WR system or Sr-Si-O-N: Eu, WR system or Sr-Ca-Si-O-N: Eu, WR is the silicon nitride fluor, but also is not limited to this.
For example, contain:
Ca-Ge-N: Eu, WR system, Sr-Ge-N: Eu, WR system, Sr-Ca-Ge-N: Eu, WR system, Ca-Ge-O-N: Eu, WR system, Sr-Ge-O-N: Eu, WR system, Sr-Ca-Ge-O-N: Eu, WR system, Ba-Si-N: Eu, WR system, Sr-Ba-Si-N: Eu, WR system, Ba-Si-O-N: Eu, WR system, Sr-Ba-Si-O-N: Eu, WR system, Ca-Si-C-N: Eu, WR system, Sr-Si-C-N: Eu, WR system, Sr-Ca-Si-C-N: Eu, WR system, Ca-Si-C-O-N: Eu, WR system, Sr-Si-C-O-N: Eu, WR system, Sr-Ca-Si-C-O-N: Eu, WR system, Mg-Si-N: Eu, WR system, Mg-Ca-Sr-Si-N: Eu, WR system, Sr-Mg-Si-N: Eu, WR system, Mg-Si-O-N: Eu, WR system, Mg-Ca-Sr-Si-O-N: Eu, WR system, Sr-Mg-Si-O-N: Eu, WR system, Ca-Zn-Si-C-N: Eu, WR system, Sr-Zn-Si-C-N: Eu, WR system, Sr-Ca-Zn-Si-C-N: Eu, WR system, Ca-Zn-Si-C-O-N: Eu, WR system, Sr-Zn-Si-C-O-N: Eu, WR system, Sr-Ca-Zn-Si-C-O-N: Eu, WR system, Mg-Zn-Si-N: Eu, WR system, Mg-Ca-Zn-Sr-Si-N: Eu, WR system, Sr-Zn-Mg-Si-N: Eu, WR system, Mg-Zn-Si-O-N: Eu, WR system, Mg-Ca-Zn-Sr-Si-O-N: Eu, WR system, Sr-Mg-Zn-Si-O-N: Eu, WR system, Ca-Zn-Si-Sn-C-N: Eu, WR system, Sr-Zn-Sn-C-N: Eu, WR system, Sr-Ca-Zn-Si-Sn-C-N: Eu, WR system, Ca-Zn-Si-Sn-C-O-N: Eu, WR system, Sr-Zn-Si-Sn-C-O-N: Eu, WR system, Sr-Ca-Zn-Si-Sn-C-O-N: Eu, WR system, Mg-Zn-Si-Sn-N: Eu, WR system, Mg-Ca-Zn-Sr-Si-Sn-N: Eu, WR system, Sr-Zn-Mg-Si-Sn-N: Eu, WR system, Mg-Zn-Si-Sn-O-N: Eu, WR system, Mg-Ca-Zn-Sr-Si-Sn-O-N: Eu, WR system, Sr-Mg-Zn-Si-Sn-O-N: Eu, the form of the fluor of the various combinations of WR system etc.
As the WR of rare earth element system, though with contain Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Lu in serve as preferably more than at least a kind, also can contain Sc, Sm, Tm, Yb.This type of rare earth element is blended in the raw material with the state of oxide compound, imide, acid amides etc. except monomeric.Rare earth element, though the electrical arrangement of stable 3 valencys of main tool, Yb, Sm etc. has 2 families, Ce, Pr, Tb etc. have the electrical arrangement of 4 valencys.When using the rare earth element of oxide compound, the participation of oxygen impacts the characteristics of luminescence of phosphor body.The situation that shortens twilight sunset is also arranged.The situation that the diffusion that promotes activator is also arranged in addition.But when using Mn, the fusing assistant effect by Mn and O increases particle diameter, and can reach the raising of luminosity.
Following embodiment is the Sr-Ca-Si-N that is added with Mn: Eu, WR, Ca-Si-N: Eu, and WR system, Sr-Si-N: Eu, WR system, Sr-Ca-Si-O-N: Eu, WR, Ca-Si-O-N: Eu, WR, Sr-Si-O-N: Eu, WR are silicon nitride.This substrate nitride phosphor is with general formula L XSi YN (2/3X+4/3Y): Eu, WR system or L XSi YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): Eu, WR (L is any of Sr, Ca, Sr and Ca) is represented.In the general formula,, also can use form arbitrarily though X and Y serve as preferred with X=2, Y=5 or X=1, Y=7.Particularly, though the substrate nitride phosphor is added with the (Sr of Mn with use XCa 1-X) 2Si 5N 8: Eu, WR, Sr 2Si 5N 8: Eu, WR, Ca 2Si 5N 8: Eu, WR, Sr XCa 1-XSi 7N 10: Eu, WR, SrSi 7N 10: Eu, WR, CaSi 7N 10: Eu, WR and the fluor represented be for preferred, but also can in the composition of this fluor, contain be selected from the group of forming by Mg, Sr, Ca, Ba, B, Al, Cu, Cr and Ni more than at least a kind.But the present invention is not limited to this embodiment and embodiment.
L is any of Sr, Ca, Sr and Ca.Sr and Ca can change proportioning according to expectation.
According to the measure of Si being used in the composition of fluor, promptly can provide the fluor of cheapness and good crystallinity.
The europium Eu of rare earth element is used at luminescence center.Europium is mainly the accurate position of the energy with 2 families and 3 valencys.Fluor of the present invention uses Eu with respect to the alkaline-earth metal silicon nitride of parent 2+And as activator.Eu 2+Be easy to oxidation, and with the Eu of 3 valencys 2O 3Composition and carry out commercially available.But, commercially available Eu 2O 3The property of participation of O is bigger, so be difficult for obtaining fabulous fluor.Therefore, use O from Eu 2O 3Removal is preferred in system's epigenesist.For example, it is preferred using europium monomer, nitrogenize europium.But, when being added with Mn, then should restriction.
Though can make Sr 2Si 5N 8: Eu, Pr, Ba 2Si 5N 8: Eu, Pr, Mg 2Si 5N 8: Eu, Pr, Zn 2Si 5N 8: Eu, Pr, Sr Si 7N 10: Eu, Pr, BaSi 7N 10: Eu, Ce, Mg Si 7N 10: Eu, Ce, ZnSi 7N 10: Eu, Ce, Sr 2Ge 5N 8: Eu, Ce, Ba 2Ge 5N 8: Eu, Pr, Mg 2Ge 5N 8: Eu, Pr, Zn 2Ge 5N 8: Eu, Pr, SrGe 7N 10: Eu, Ce, BaGe 7N 10: Eu, Pr, MgGe 7N 10: Eu, Pr, ZnGe 7N 10: Eu, Ce, Sr 1.8Ca 0.2Si 5N 8: Eu, Pr, Ba 1.8Ca 0.2Si 5N 8: Eu, Ce, Mg 1.8Ca 0.2Si 5N 8: Eu, Pr, Zn 1.8Ca 0.2Si 5N 8: Eu, Ce, Sr 0.8Ca 0.2Si 7N 10: Eu, La, Ba 0.8Ca 0.2Si 7N 10: Eu, La, Mg 0.8Ca 0.2Si 7N 10: Eu, Nd, Zn 0.8Ca 0.2Si 7N 10: Eu, Nd, Sr 0.8Ca 0.2Ge 7N 10: Eu, Tb, Ba 0.8Ca 0.2Ge 7N 10: Eu, Tb, Mg 0.8Ca 0.2Ge 7N 10: Eu, Pr, Zn 0.8Ca 0.2Ge 7N 10: Eu, Pr, Sr 0.8Ca 0.2Si 6GeN 10: Eu, Pr, Ba 0.8Ca 0.2Si 6GeN 10: Eu, Pr, Mg 0.8Ca 0.2Si 6GeN 10: Eu, Y, Zn 0.8Ca 0.2Si 6GeN 10: Eu, Y, Sr 2Si 5N 8: Pr, Ba 2Si 5N 8: Pr, Sr 2Si 5N 8: Tb, BaGe 7N 10: Ce etc., but be not limited to this.
The Mn of additive can promote Eu 2+Diffusion, and can reach the raising of the luminous efficiency of luminosity, energy efficiency, quantum yield etc.Mn contains in raw material, or Mn monomer or Mn compound are contained in manufacturing process, and all burns till processing with raw material.But Mn does not contain in the substrate nitride phosphor after burning till, even or contain, also amount is only remaining a small amount of more originally.This is to be regarded as in firing process, the cause of dispersing because of Mn.
Fluor in the substrate nitride phosphor, or the low nitride phosphor of base all contain be selected from the group of forming by Mg, Sr, Ba, Zn, Ca, Ga, In, B, Al, Cu, Li, Na, K, Re, Ni, Cr, Mo, O and Fe more than at least a kind.This type of element has the effect that increases particle diameter, raising luminosity etc.In addition, B, A1, Mg, Cr and Ni have the effect that can suppress twilight sunset.Usually, be not added with the fluor of the additive of B, Mg, Cr etc., be added with the fluor of additive, the more needed time of 1/10 twilight sunset can be foreshortened to 1/4 degree from 1/2.
The fluor 11 of present embodiment 3 absorbs by luminous element 10 and the part of luminous blueness system, and carries out the light in yellow to red zone luminous.This fluor 11 is used at the light-emitting device with above-mentioned formation, and according to by luminous element 10 and the colour mixture of the red colour system of luminous blueness system and fluor, and the luminous light-emitting device of white color system that provides warm colour to be.
Particularly fluor 11 contains with cerium activated yttrium except fluor of the present invention. and aluminum oxide is that fluor serves as preferred.By containing above-mentioned yttrium. aluminum oxide is the measure of fluor, promptly can be adjusted to the colourity of expectation.With cerium activated yttrium. aluminum oxide is a fluor, absorbs by luminous element 10 and the part of luminous blueness system, and carries out the light of yellow area luminous.Herein, according to the blueness luminous system and yttrium by luminous element 10. it is luminous that aluminum oxide is that the colour mixture of the sodium yellow of fluor is carried out blue white white color system.Therefore, with this yttrium. aluminum oxide is fluor and above-mentioned fluor and fluor 11 and the measure of luminous blueness system combination by luminous element 10 that the coating member with light transmission is mixed together, and the light-emitting device of the white color system of warm colour system promptly can be provided.The light-emitting device of the white color system of this warm colour system, it is 75 to 95 that number Ra is estimated in its average colour developing, colour temperature is 2000 to 8000K.It is the white color system light-emitting device that is positioned on the track of blackbody radiation of chromaticity diagram that number Ra and colour temperature are estimated in preferred average especially colour developing.But, because the colour temperature of expectation and the light-emitting device that number is estimated in average colour developing are provided, and so also can be suitably to change yttrium. aluminum oxide is the use level of fluorescent substance and fluor.The white color system light-emitting device of this warm colour system can reach the improvement that number R9 is estimated in special colour developing.Blue based light-emitting device in the past and with cerium activated yttrium. aluminum oxide is the luminous light-emitting device of white color system of the combination of fluorescent substance, and its special colour developing is estimated number R9 roughly closely 0, and red composition is inadequate.Therefore, improve special colour developing evaluation number R9 and become the solution problem, but by fluor of the present invention is contained at yttrium. aluminum oxide is the measure in the fluorescent substance, promptly special colour developing can be estimated number R9 and be increased to 60 to 70.
(manufacture method of fluor)
Then, use Figure 13 and the fluor Sr-Ca-Si-O-N of present embodiment: Eu is described, the manufacture method of La, but be not limited to this manufacture method.Above-mentioned fluor contains Mn.
Sr, the Ca of raw material are pulverized (P1).It is preferred that the Sr of raw material, Ca use monomer, but also can use the compound of imide compound, amide compound etc.In addition, raw material Sr, Ca also can contain B, Al, Cu, Mg, MnO, Mn 2O 3, Al 2O 3The Sr that obtains via pulverizing, Ca, about 0.1 μ m to the 15 μ m of its median size are preferred, but are not limited to this scope.The purity 2N of Sr, Ca is above to be preferred, but is not limited to this.In order more to improve its admixture,, after nitrogenize, the pulverizing, use as raw material so also can in metal Ca, metal Sr, metal Eu, make more than at least 2 kinds after the alloy state.
The Si of raw material is pulverized (P2).It is preferred that the Si of raw material uses monomer, but also can use nitride-based compound, imide compound, amide compound etc.For example, Si 3N 4, Si (NH 2) 2, Mg 2Si etc.The purity 3N of the Si of raw material is above to be preferred, but also can contain Al 2O 3, Mg, metal boride (Co 3B, Ni 3B, CrB), manganese oxide, H 3BO 3, B 2O 3, Cu 2The compound of O, CuO etc.About 0.1 μ m to the 15 μ m of the median size of Si compound is preferred.
Then, in nitrogen atmosphere, Sr, the Ca of raw material carried out nitrogenize (P3).This reaction formula is shown in formula 4.
(formula 4)
In nitrogen atmosphere, with 600～900 ℃ with the about nitrogenize of Sr, Ca 5 three o'clock.Sr, Ca can mix the back nitrogenize, but also can each carry out nitrogenize respectively.Must obtain the nitride of Sr, Ca therefrom.The nitride of Sr, Ca is highly purified to be preferred, but also can use commercially available.
In nitrogen atmosphere, the Si of raw material is carried out nitrogenize (P4).This reaction formula is shown in formula 5.
(formula 5)
Silicon Si is also in nitrogen atmosphere, with about 5 hours of 800～1200 ℃ of about nitrogenize.Obtain silicon nitride therefrom.Silicon nitride used in the present invention is highly purified to be preferred.But also can use commercially available.
The nitride of Sr, Ca or Sr-Ca is pulverized (P5),
In the same manner, the nitride of Si is pulverized (P6).
In addition, similarly, with the compd E u of Eu 2O 3Pulverize (P7).As the compound of Eu, can use europium sesquioxide, also but can use metal europium, nitrogenize europium etc.Europium sesquioxide is highly purified to be preferred, but also can use commercially available.
In above-mentioned raw materials, also can contain be selected from the group of being economized by Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, O and Ni more than at least a kind.In addition, also can be in following mixed processes (P8), regulate use level and the above-mentioned element of Mg, Zn, B etc. is mixed.This type of compound also can single-alonely be added in the raw material, but normally adds with the form of compound.This compound has H 3BO 3, Cu 2O 3, MgCl 2, MgO. CaO, Al 2O 3, metal boride (CrB, Mg 3B 2, AlB 2, MnB), B 2O 3, Cu 2O, CuO etc.
Compound L a with La 2O 3Pulverize (P8).
Lanthanum trioxide then promptly replaces carbonate, so pulverize in being placed on air the time in nitrogen atmosphere.Lanthanum trioxide is highly purified for preferred, but also can use commercially available.About 0.1 μ m to the 15 μ m of the median size of the nitride of the alkaline-earth metal after the pulverizing, silicon nitride and europium sesquioxide, lanthanum trioxide is preferred.
After carrying out above-mentioned pulverizing, with the nitride of Sr, Ca, Sr-Ca, the nitride of Si, the compd E u of Eu 2O 3, La compound L a 2O 3Mix and interpolation Mn 2O 3(P9).
At last, in nitrogen atmosphere, with the nitride of Sr, Ca, Sr-Ca, the nitride of Si, the compd E u of Eu 2The compound L a of the mixture of O, La 2O 3Burn till processing (P10).Can obtain being added with the Sr-Ca-Si-O-N of Mn: Eu La and the fluor (P11) represented by burning till.To be shown in formula 6 according to this reaction formula that burns till the substrate nitride phosphor that produces.
(formula 6)
But,, promptly can change composition as the fluor of its purpose by changing the cooperation ratio of each raw material.
Firing temperature can burn till 1200 to 1700 ℃ scope, but serves as preferred with 1400 to 1700 ℃ firing temperature.Burning till use heats up lentamente, and carry out stage that a few hours burn till with 1200 to 1500 ℃ and burn till to preferably, carry out burning till of fs but also can use with 800 to 1000 ℃, and heating and burn till (multistage burns till) with 1200 to 1500 ℃ of two-stages of burning till of carrying out subordinate phase lentamente.The raw material of fluor 11 uses the crucible of boron nitride (BN) material, boat (baot) and burning till to preferably.Outside the crucible of boron nitride material, also can use aluminium (Al 2O 3) crucible of material.
By using above manufacture method, promptly can obtain fluor as purpose.
Embodiment 4
The light-emitting device of the light-emitting device Class1 of embodiments of the present invention 4, and contain fluor described later.
Detailed description relates to the component parts of light-emitting device of the present invention.
It is silicon nitride that the fluor of present embodiment 4 is added with the Sr-Ca-Si-N of Mn: R, Ca-Si-N: R, Sr-Si-N: R, Sr-Ca-Si-O-N: R, Ca-Si-O-N: R, Sr-Si-O-N: R.This substrate nitride phosphor is with general formula L XSi YN (2/3X+4/3Y): R or L XSi YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): (L is any of Sr, Ca, Sr and Ca to R.0.5≤X≤3,1.5≤Y≤8) represented.In the general formula,, also can use form arbitrarily though X and Y serve as preferred with X=2, Y=5 or X=1, Y=7.Particularly, the substrate nitride phosphor is though be added with (the Sr of Mn with use XCa 1-X) 2Si 5N 8: R, Sr 2Si 5N 8: R, Ca 2Si 5N 8: R, Sr XCa 1-XSi 7N 10: R, SrSi 7N 10: R, CaSi 7N 10: R and the fluor of expression be preferably, but also can in the composition of this fluor, contain be selected from the group of forming by Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni more than at least a kind.But the present invention is not limited to this embodiment and embodiment.
L is any of Sr, Ca, Sr and Ca.Sr and Ca can change proportioning according to expectation.
According to the measure of Si being used in the composition of fluor, promptly can provide the fluor of cheapness and good crystallinity.
The R (preferably going up europium Eu) of rare earth element is used at luminescence center.Europium mainly has the accurate position of energy of 2 families and 3 valencys.Fluor of the present invention uses rare earth element R (to be preferably Eu with respect to the alkaline-earth metal silicon nitride of parent 2+) and as activator.For example, use europium monomer, nitrogenize promising preferred.But when being added with Mn, then should restriction.
The Mn of additive can promote activator R (Eu for example 2+) diffusion, and can reach the raising of the luminous efficiency of luminosity, energy efficiency, quantum yield etc.Mn contains in raw material, or Mn monomer or Mn compound are contained in manufacturing process, and all burns till processing with raw material.But Mn does not contain in the substrate nitride phosphor after burning till, even or contain, also amount is only remaining a small amount of more originally.This is to be regarded as in firing process, the cause of dispersing because of Mn.
Fluor in the substrate nitride phosphor, or the substrate nitride phosphor all contain be selected from the group of forming by Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, O and Ni more than at least a kind.This type of element has the effect that increases particle diameter, raising luminosity etc.In addition, B, Al, Mg, Cr and Ni have the effect that can suppress twilight sunset.Usually, be not added with the fluor of the additive of B, Mg, Cr etc., be added with the fluor of additive, more can with the needed time of 1/10 twilight sunset from 1/2 foreshorten to 1/4 degree till.
Fluor 11 of the present invention absorbs by luminous element 10 and the part of luminous blueness system, and carries out the light in yellow to red zone luminous.This fluor 11 used have the light-emitting device of above-mentioned formation, and according to by luminous element 10 and the colour mixture of the red colour system of luminous blueness system and fluor, and the luminous light-emitting device of white color system that provides warm colour to be.
Particularly fluor 11 contains with cerium activated yttrium except fluor of the present invention. and aluminum oxide is that fluor serves as preferred.By containing above-mentioned yttrium. aluminum oxide is the measure of fluorescent substance, promptly can be adjusted to the colourity of expectation.With cerium activated yttrium. aluminum oxide is a fluorescent substance, absorbs by luminous element 10 and the part of luminous blueness system, and carries out the light of yellow area luminous.Herein, according to the blueness luminous system and yttrium by luminous element 10. it is luminous that aluminum oxide is that the colour mixture of the sodium yellow of fluorescent substance is carried out blue white white color system.Therefore, with this yttrium. aluminum oxide fluorescent substance and above-mentioned fluor and fluor 11 and the measure of luminous blueness system combination by luminous element 10 that the coating member with light transmission is mixed together promptly can provide the light-emitting device of the white color system of warm colour system.The light-emitting device of the white color system of this warm colour system, it is 75 to 95 that number Ra is estimated in its average colour developing, colour temperature is 2000 to 8000K.It is the light-emitting device that is positioned at the white color system on the track of blackbody radiation of chromaticity diagram that preferred especially average color is estimated number Ra and colour temperature, but because the colour temperature of expectation and the light-emitting device that number is estimated in average colour developing are provided, and so also can be suitably to change yttrium. aluminum oxide is the use level of fluorescent substance and fluor.The light-emitting device of the white color system of this warm colour system can reach the improvement that number R9 is estimated in special colour developing.Blue based light-emitting device in the past and the yttrium that is activated with cerium. aluminum oxide is the luminous light-emitting device of coloured light of the combination of fluorescent substance, and its special colour developing is estimated number R9 roughly closely 0, and red composition is inadequate.Therefore, improve special colour developing evaluation number R9 and become problem, but by fluor of the present invention is contained at yttrium. aluminum oxide is the measure in the fluorescent substance, promptly can comment board R9 to be increased to till 60 to 70 special colour developing.
(manufacture method of fluor)
Then, use Figure 21 and fluor ((Sr of the present invention is described XCa 1-X) 2Si 5N 8: manufacture method Eu), but be not limited to this manufacture method.Contain Mn, O in the above-mentioned fluor.
Sr, the Ca of raw material are pulverized (P1).It is preferred that the Sr of raw material, Ca use monomer, but also can use the compound of imide compound, amide compound etc.In addition, raw material Sr, Ca also can contain B, Al, Cu, Mg, Mn, Al 2O 3Deng.The Sr of raw material, C pulverize in the spherical case in argon atmospher.The Sr that obtains via pulverizing, Ca, about 0.1 μ m to the 15 μ m of its median size are preferred, but are not limited to this scope.The purity 2N of Sr, Ca is above to be preferred, but is not limited to this.Owing to more improve admixture, after also can in metal Ca, metal Sr, metal Eu, making alloy state more than at least 1, after nitrogenize, the pulverizing, use as raw material.
The Si of raw material is pulverized (P2).It is preferred that the Si of raw material uses monomer, but also can use nitride-based compound, imide compound, amide compound etc.For example, Si 3N 4, Si (NH 2) 2, Mg 2Si etc.The purity 3N of the Si of raw material is above to be preferred, but also can contain Al 2O 3, Mg, metal boride (Co 3B, Ni 3B, CrB), manganese oxide, H 3BO 3, B 2O 3, Cu 2The compound of O, CuO etc.About 0.1 μ m to the 15 μ m of the median size of Si compound is preferred.
Then, in nitrogen atmosphere, Sr, the Ca of raw material carried out nitrogenize (P3).This reaction formula is shown in formula 7.
(formula 7)
In nitrogen atmosphere, with 600～900 ℃ with the about nitrogenize of Sr, Ca 5 hours.Sr, Ca can mix and nitrogenize, also can each carry out nitrogenize respectively.Thus, promptly can obtain the nitride of Sr, Ca.The nitride of Sr, Ca is highly purified to be preferred, but also can use commercially available.
In nitrogen atmosphere, the Si of raw material is carried out nitrogenize (P4).This reaction formula is shown in formula 8.
(formula 8)
Silicon Si is also in nitrogen atmosphere, with 800～1200 ℃ of about nitrogenize 5 hours.Can obtain silicon nitride thus, silicon nitride used in the present invention is highly purified to be preferred, but also can use commercially available.
The nitride of Sr, Ca or Sr-Ca is pulverized (P5).
Similarly, the nitride of Si is pulverized (P6).
In addition, similarly with the compd E u of Eu 2O 3Pulverize (P7).As the compound of Eu, can use europium sesquioxide, but also can use the metal europium, nitrogenize europium etc.In addition, the R of raw material also can be to use imide compound, amide compound.The europium sesquioxide high purity is preferred, but also can use commercially available.About 0.1 μ m to the 15 μ m of the median size of the nitride of the alkaline-earth metal after the pulverizing, silicon nitride and europium sesquioxide is preferred.
In above-mentioned raw materials, also can contain be selected from the group of forming by Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, O and Ni more than at least a kind.In addition, also can be in following mixed processes (P8), regulate use level and the above-mentioned element of Mg, Zn, B etc. is mixed.This type of compound also can be added in the raw material separately, but adds with the form of compound usually.This kind compound H 3BO 3, Cu 2O 3, MgC1 2, MgO.CaO, Al 2O 3, metal boride (CrB, Mg 3B 2, A1B 2, MnB), B 2O 3, Cu 2O, CuO etc.
After carrying out above-mentioned pulverizing, with the nitride of Sr, Ca, Sr-Ca, the nitride of Si, the compd E u of Eu 2O 3Mix, and add Mn (P8).
At last in ammonia atmosphere, with the nitride of Sr, Ca, Sr-Ca, the nitride of Si, the compd E u of Eu 2O 3Mixture burn till (P9).Can obtain to be added with (the Sr of Mn by burning till XCa 1-x) 2Si 5N 5: the fluor (P10) that Eu is represented.To be shown in formula 9 according to this reaction formula that burns till the substrate nitride phosphor that produces.
(formula 9)
But,, promptly can change composition as the fluor of purpose by changing the cooperation ratio of each raw material.
Firing temperature can burn till 1200 to 1700 ℃ scope, but 1400 to 1700 ℃ firing temperature is preferred.Burn till that use slowly heats up and carry out stage that a few hours burn till with 1200～1500 ℃ and burn till to preferably, carry out burning till of fs but also can use with 800 to 1000 ℃, and heating and burn till (multistage burns till) with 1200 to 1500 ℃ of two-stages of burning till of carrying out subordinate phase lentamente.The raw material of fluor 11 uses the crucible, boat of boron nitride (BN) material and burns till to preferably.Outside the crucible of boron nitride material, also can use aluminium (Al 2O 3) crucible of material.
By using above manufacture method, promptly can obtain fluor as purpose.
Embodiment 5
The light-emitting device of present embodiment 5 uses luminous element with near the luminescent spectrum the 460nm and fluor described later and the light-emitting device of the Class1 that constitutes.
(fluor of embodiment 5)
The nitride phosphor of present embodiment 5 contains at least with L XM YN (2/3X+4/3Y): the substrate nitride phosphor that R is represented, and contain the nitride phosphor more than at least a kind that is selected from the group of being formed by Mg, Sr, Ba, Zn, B, Al, Cu, Mn, Cr, O and Fe etc.
L contain be selected from the group of being formed by the II valency of Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg more than at least a kind.Owing to can provide to be difficult to decompose and to trust the high nitride phosphor of letter, so use Mg, Ca, Sr, Ba are preferred.Except only can use a kind this type of the formation element, also can be to constitute element and to change this part of a kind with other.
M contain be selected from the group of being formed by the IV valency of C, Si, Ge, Sn, Ti, ZR, Hf more than at least a kind.Particularly by M being made the nitride phosphor that Si can provide cheapness and good crystallinity.
R is an activator, and contains and be selected from more than at least a in the group of being made up of Eu, Cr, Mn, Pb, Sb, Ce, Tb, Pr, Sm, Tm, Ho, Er, Yb, Nd.Wherein, carry out luminous Eu, Mn, Ce etc. to red area and explanation the present invention, be not limited to this though use with yellow.Eu is used the system at R, and the europium Eu of rare earth element is made luminescence center.Europium is mainly the accurate position of the energy with 2 families and 3 valencys.Nitride phosphor of the present invention uses Eu with respect to the alkaline-earth metal silicon nitride of parent 2+And as activator.Eu 2+Be easy to oxidized, and with the Eu of 3 valencys 2O 3Composition carry out commercially available.Owing to use Eu 2O 3, and the situation of the diffusion that promotes activator is also arranged.It is preferred using europium monomer, nitrogenize europium.
Nitride phosphor except the substrate nitride phosphor, also contain be selected from the group of being formed by Mg, Sr, Ba, Zn, Ca, Ga, In, B, Al, Cu, Mn, Li, Na, K, Re, Ni, Cr, Mo, O and Fe etc. more than at least a kind.This type of element has the effect that increases particle diameter, raising luminosity etc.In addition, B, Mg, Cr, Ni, Al have the effect that suppresses twilight sunset.Usually, be added with the fluor aspect of additives such as B, Mg, Cr, be not added with the fluor of additive, more 1/10 twilight sunset time necessary can be foreshortened to till 1/4 from 1/2.On the other hand, Fe, Mo have the anxiety that reduces luminous efficiency, are preferred outside system so remove.
Nitride phosphor 11 absorbs by semiconductor light-emitting elements 10 and the part of luminous blueness system, and carries out the light in yellow to red zone luminous.Use this nitride phosphor 11 having the light-emitting device of above-mentioned formation, and according to by semiconductor luminous element 10 and the colour mixture of the red colour system of luminous blueness system and nitride phosphor, and the luminous light-emitting device of the white color system that warm colour is is provided.
Particularly fluor 11 contains the yttrium that is activated with cerium except nitride phosphor of the present invention. and aluminum oxide is that fluorescent substance serves as preferred.By containing above-mentioned yttrium. aluminum oxide is a fluorescent substance, promptly can be adjusted to the colourity of expectation.The yttrium that is activated with cerium. aluminum oxide is a fluorescent substance, absorbs by semiconductor light-emitting elements 10 and the part of luminous blueness system, and carries out the light of yellow area luminous.Herein, according to blueness system and the yttrium luminous by semiconductor light-emitting elements 10. aluminum oxide is that the colour mixture of the sodium yellow of fluorescent substance is carried out the luminous of the white white color system of indigo plant.Therefore, by with this yttrium. aluminum oxide is fluorescent substance and above-mentioned nitride phosphor and fluor 11 and the luminous blueness system combination by semiconductor light-emitting elements 10 that the coating member with light transmission is mixed together, and the light-emitting device of the white color system of warm colour system promptly can be provided.The light-emitting device of the white color system of this warm colour system, it is 75 to 95 that number Ra is estimated in its average colour developing, colour temperature is 2000 to 8000K.It is the light-emitting device that is positioned at the white color system on the track of blackbody radiation of chromaticity diagram that number Ra and colour temperature are estimated in preferred average especially colour developing.But, because the colour temperature of expectation and the light-emitting device that number is estimated in average colour developing are provided, and so can suitably change yttrium. aluminum oxide is the use level of fluorescent substance and nitride phosphor.
(manufacture method of nitride phosphor)
Then, use Figure 33 and the manufacture method of nitride phosphor of the present invention is described.
The L of raw material and Mg etc. are pulverized (P1).The L of raw material contain be selected from the group of being formed by the II valency of Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg more than at least a kind.Particularly the alkaline-earth metal be made up of the group of Be, Mg, Ca, Sr, Ba of the L of raw material is for preferred, and then serve as preferably with the alkaline-earth metal monomer, but also can contain more than 2.The L of raw material also can be to use imide compound, amide compound etc.In addition, raw material L also can contain B, Al, Cu, Mg, Mn, Al 2O 3Deng.The alkaline-earth metal that obtains via pulverizing, about 0.1 μ m to the 15 μ m of its median size are preferred, but are not limited to this scope.The purity 2N of L is above to be preferred, but is not limited to this.Owing to more improve admixture, thus with the activator of the M of the L of metal, metal, metal make alloy state more than at least a kind after, also can carry out nitrogenize, pulverize the back and use as raw material.
The Si of raw material and Al etc. are pulverized (P2).Substrate nitride phosphor L XM YN (2/3X+4/3Y): the M of R system, contain be selected from the group of being formed by the IV valency of C, Si, Ge, Sn more than at least a kind.The M of raw material also can be to use imide compound, amide compound etc.Because cheap and be easy to handle, so use Si manufacture method be described, but be not limited to this among the M.Also can use Si, Si 3N 4, Si (NH 2) 2, Mg 2Si etc.Al 2O 3Outside, also can contain Mg, metal boride (Co 3B, Ni 3B, Mo 2B), manganese oxide, H 3BO 3, B 2O 3, Cu 2The compound of O, CuO etc.About 0.1 μ m to the 15 μ m of the median size of Si compound is preferred.More than the purity 3N of Si.
Then, in nitrogen atmosphere, the L of raw material and Mg etc. are carried out nitrogenize (P3).This reaction formula is shown in formula 10.Because the several 10～1000ppm grades of Mg are not so contain at reaction formula.
(formula 10)
In nitrogen atmosphere, with the L of II valency with 600～900 ℃ of about nitrogenize 5 hours.Thus, promptly can obtain the nitride of L.The nitride of L is highly purified to be preferred, but also can use commercially available.
In nitrogen atmosphere, the Si of raw material and Al etc. are carried out nitrogenize (P4).
This reaction formula is shown in formula 11.In addition, also owing to the several 10～1000ppm grades of Al, so do not contain at reaction formula.
(formula 11)
Also in nitrogen atmosphere, with 800～1200 ℃, approximately nitrogenize is 5 hours for silicon Si.Thus, promptly can obtain silicon nitride.Silicon nitride high purity used in the present invention is preferred, but also can use commercially available.
The nitride of L and Mg etc. is pulverized (P5).
Equally, the nitride of Si and Al etc. is pulverized (P6).
In addition, in the same manner with the compd E u of Eu 2O 3Pulverize (P7).Substrate nitride phosphor L XM YN (2/3X+4/3Y): the R of R is an activator, and contains and be selected from more than at least a in the group of being made up of Eu, Cr, Mn, Pb, Sb, Ce, Tb, Pr, Sm, Tm, Ho, ER.Represent the Eu of emission wavelength and manufacture method of the present invention is described at red area among using R, but be not limited to this.Compound as Eu uses europium sesquioxide, but also can use metal europium, nitrogenize europium etc.In addition, the R of raw material also can use imide compound, amide compound.The europium sesquioxide high purity is preferred, but also can use commercially available.The median size of the nitride of the alkaline-earth metal after the pulverizing, silicon nitride and europium sesquioxide, about 0.1 μ m to 15 μ m is preferred.
In above-mentioned raw materials, contain be selected from the group of being formed by Mg, Sr, Ba, Zn, Ca, Ga, In, B, Al, Cu, Mn, Li, Na, K, Re, Ni, Cr, Mo, O and Fe etc. more than at least a kind.In addition, also can be in following mixed processes (P8), regulate use level and will be selected from compound in the group of B, Al, Mn etc.This type of compound also can be added in the raw material separately, but adds with the form of compound usually.This kind compound H 3BO 3, Cu 2O 3, MgCl 2, MgO.CaO, Al 2O 3, metal boride (CrB, Mg 3B 2, AlB 2, MnB), B 2O 3, Cu 2O, CuO etc.In addition, Mn, Al etc. contains in the raw material before burning till, and the conversion part of raw materials.
After carrying out above-mentioned pulverizing, with the nitride of nitride, Si and the Al etc. of L and Mg etc., the compd E u of Eu 2O 3Deng mixing (P8).
At last in ammonia atmosphere, with the nitride of nitride, Si and the Al etc. of L and Mg etc., the compd E u of Eu 2O 3Deng mixture burn till (P9).Via burn till can obtain to contain Mg, Al etc. with L XM YN (2/3X+4/3Y): the fluor (P10) that Eu is represented.To be shown in formula 1 according to this reaction formula that burns till the nitride phosphor that produces.With in the same manner above-mentioned, also owing to Mg, Al, H 3BO 3Deng the several 10～1000ppm grades of additive, so do not contain in reaction formula.
(formula 12)
But by the composition of change as the fluor of purpose, then the mixture ratio of each mixture can suitably change.Substrate nitride phosphor L XM YN (2/3X+4/3Y): R is L 2Si 5N 8: Eu, LSi 7N 10: Eu is preferred, but is not limited to this use level.
Firing temperature can burn till 1200 to 1700 ℃ scope, more preferably then is 1200 to 1400 ℃ firing temperature.Burn till that use heats up lentamente and carry out stage that a few hours burn till with 1200 to 1500 ℃ and burn till to preferably, carry out burning till of fs but also can use with 800 to 1000 ℃, and heating and carry out the two-stage that subordinate phase burns till with 1200 to 1500 ℃ and burn till (multistage burns till) lentamente.The raw material of fluor 11 uses the crucible, boat of boron nitride (BN) material and burns till to preferably.Outside the crucible of boron nitride material, also can use aluminum oxide (Al 2O 3) crucible of material.
By using above manufacture method, promptly can obtain fluor as purpose.
Embodiment 6
The nitride phosphor that the light-emitting phosphor device of embodiment 6 is used, and as following formation.
At first, use Figure 43 and the manufacture method of the nitride phosphor of present embodiment 6 is described.Operation P1 pulverizes the L of raw material.
The L of raw material contain be selected from the group of being formed by the II valency of Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg more than at least a kind.The L of raw material particularly, the alkaline-earth metal of being made up of the group of Be, Mg, Ca, Sr, Ba be for preferred, and then serve as preferably with the alkaline-earth metal monomer, but also can contain more than 2.The L of raw material also can use imide compound, amide compound etc.The alkaline-earth metal that obtains via pulverizing, about 0.1 μ m to the 15 μ m of its median size are preferred, but are not limited to this scope.The purity 2N of L is above to be preferred, but is not limited to this.Owing to more can improve admixture, so after also can in the activator of the M of the L of metal, metal, metal, making alloy state at least 1 or more, after nitrogenize, the pulverizing, use as raw material.
Operation P2 pulverizes the Si of raw material.Substrate nitride phosphor L XM YN (2/3X+4/3Y): the M of R system, contain be selected from the group of being formed by the IV valency of C, Si, Ge, Sn more than at least a kind.The M of raw material also can be to use imide compound, amide compound etc.Among the M, since cheap and be easy to handle, so use Si manufacture method is described, but is not limited to this.Also can use Si, Si 3N 4, Si (NH 2) 2Deng.About 0.1 μ m to the 15 μ m of the median size of Si compound is preferred.The purity 3N of Si is above to be preferred.
Operation P3 carries out nitrogenize with the L of raw material in nitrogen atmosphere.This reaction formula is shown in formula 13.
(formula 13)
With the L of II valency in nitrogen atmosphere, 600～90O ℃ of about nitrogenize 5 hours.Promptly can obtain the nitrogenize brick thus.Silicon nitride high purity used in the present invention is preferred, but also can use commercially available (high-purity chemical system).
Operation P4 carries out nitrogenize with the Si of raw material in nitrogen atmosphere.This reaction formula is shown in formula 14.
(formula 14)
Silicon Si is also in nitrogen atmosphere, with 800～1200 ℃ of about nitrogenize 5 hours.Promptly can obtain silicon nitride thus.Silicon nitride high purity used in the present invention is preferred, but also can use commercially available (word portion system).
Operation P5 is with the nitride L of L 3N 2Pulverize.
Operation P6 is for silicon nitride Si 3N 4Also pulverize.
Operation P7 is with the compd E u of Eu 2O 3Also pulverize.
Substrate nitride phosphor L XM YN (2/3X+4/3Y): the R of R is an activator, and contains and be selected from more than at least a in the group of being made up of Eu, Cr, Mn, Pb, Sb, Ce, Tb, Pr, Sm, Tm, Ho, ER.Use among the R at red area and carry out luminous Eu and illustrate and relate to manufacture method of the present invention, but be not limited to this.As the compound of Eu and use europium sesquioxide, but also can use the nitrogenize europium.In addition, the R of raw material also can use imide compound, amide compound.The europium sesquioxide high purity is preferred, but also can be to use commercially available (SHIN-ETSU HANTOTAI's system).The median size of the nitride of the alkaline-earth metal after the pulverizing, silicon nitride and europium sesquioxide, about 0.1 μ m to 15 μ m is preferred.
Operation P8 is after carrying out above-mentioned pulverizing, with L 3N 2, Si 3N 4, Eu 2O 3Mix.
This type of mixture is oxidized because of being easy to, so in Ar atmosphere, or mix in the spherical case in the nitrogen atmosphere.
At last at operation P9, in ammonia atmosphere, with L 3N 2, Si 3N 4, Eu 2O 3Mixture burn till.
By burning till, promptly can obtain with L as purpose XSi YThe fluor (P10) that NZ: Eu is represented.This is burnt till the reaction formula that is produced be shown in formula 15.
(formula 15)
But by the composition of change as the fluor of purpose, then the mixture ratio of each mixture can suitably change.In formula 15, oxygen is contained at nitride phosphor of the present invention, but owing to can reach purpose of the present invention, so nitride phosphor contains substrate nitride phosphor L XM YN (2/3X+4/3Y): R gets final product.
Burn till processing and can use tube furnace, box-type furnace, high frequency furnace, metal furnaces etc.Firing temperature can burn till 1200 to 1600 ℃ scope, but more preferably 1200 to 1400 ℃ firing temperature.Use boron nitride (BN) material, be preferred.Outside the crucible of boron nitride material, also can use aluminum oxide (Al 2O 3) crucible of material.Even this is because when using the crucible of aluminum oxide material, in ammonia atmosphere, do not hinder luminous yet.
According to above manufacture method, promptly can make the fluor of embodiment 6, and can obtain fluor as purpose.
Below, at nitride phosphor, the L of present embodiment 6 XSi YIn the manufacture method of the nitride phosphor of NZ: Eu, present embodiment 6, the nitride of the L that relates to this synthetic intermediate, the nitride of M, the compound of R are described.As the nitride of L and to lift alkaline-earth metal be example, as the nitride of M and to lift silicon nitride be example, as the compound of R and lift europium sesquioxide and illustrate, but be not limited to this for example.
The R of the nitride phosphor of present embodiment 6 is with the Eu making luminescence center of rare earth element.Europium is mainly the accurate position of the energy with divalent and 3 valencys.Nitride phosphor of the present invention uses Eu with respect to the alkaline-earth metal silicon nitride of parent 2+And as activator.Eu 2+Be easy to oxidized, and with the Eu of 3 valencys 2O 3Composition carry out commercially available.Wherein, commercially available Eu 2O 3The participation of O is bigger, and is difficult for obtaining fabulous fluor.Therefore, use O from Eu 2O 3And remove system outside preferably.For example, it is preferred using europium monomer, nitrogenize europium.
The L of the II valency of raw material also is easy to oxidized.For example, commercially available Ca metal contains 0.66% O, 0.01% N.Owing in manufacturing process, this Ca metal is carried out nitrogenize, so buy the CaCl2 Ca of commercially available (high-purity chemical system) 3N 2, and when measuring O and N, O is 1.46%, N is 16.98%, but airtight once again and when leaving standstill for 2 weeks after the Kaifeng, then changes over O and be 6.80%, N is 13.20%.In addition, commercially available in addition CaCl2 Ca 3N 2O is 26.25%, N is 6.54%.This O becomes impurity and produces the situation of luminous deterioration, is preferred outside system so remove with doing one's utmost.Therefore, in nitrogen atmosphere, carry out the nitrogenize of 8 hours calcium with 800 ℃.Its result promptly can obtain the O in the CaCl2 is reduced to till 0.67%.N15.92% in the CaCl2 of this moment.
Comparative experiments
For the feature that makes present embodiment 6 is tending towards clearly, so manufacturing alkaline-earth metal silicon nitride fluor Ca in the past 2Si 5N 8: Eu also measures.Its test-results is shown in table 31.
Table 31
Raw material The result
The basic comprising element Raw material ratio of mixture (Ca/Si/Eu) Burn till pattern Atmosphere Shape Body colour Visual luminous (365nm) Remarks
Comparative example 5 Ca 2Si 5N 8∶Eu 2/5/0.2 1400 ℃ * 5 hours 1 stage H 2/N 2 Crucible Orange (part) Orange (part)
Comparative example 6 Ca 2Si 5N 8∶Eu 1.8/5/0.2 1400 ℃ * 5 hours 1 stage H 2/N 2 Boat White Not luminous Increment, oxidation is arranged
Comparative example 7 Ca 2Si 5N 8∶Eu 1.8/5/0.2 1400 ℃ * 5 hours 1 stage H 2/N 2 Crucible Yellow (part) Yellow (part) It is surface light emitting
Comparative example 8 Ca 2Si 5N 8∶Eu 4/5/0.2 1400 ℃ * 5 hours 1 stage H 2/N 2 Crucible Orange (part) Orange (part) Increment, oxidation is arranged
Comparative example 9 Ca 2Si 5N 8∶Eu 1.8/5/0.2 1400 ℃ * 5 hours 1 stage H 2/N 2 Crucible White Not luminous
Comparative example 5 is fluor Ca in the past 2Si 5N 8: Eu.
The CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Cooperation ratio (mol ratio), can be adjusted into Ca: Si: Eu=2: 5: 0.2.This 3 raw materials of compound is loaded to the BN crucible,, uses small-sized stove to carry out burning till in 5 hours with under 1400 ℃, hydrogen/nitrogen atmosphere.Temperature is crossed over 5 hours and is heated to 1400 ℃ lentamente from room temperature, and after carrying out burning till in 5 hours with 1400 ℃, and then crosses over 5 hours and cool off till room temperature lentamente.Its result, body colour are orange, luminously also obtain orange fluor powder, but when carrying out visual inspection, luminosity is extremely low.
Change the firing condition of stove, firing temperature, atmosphere, shape and compare burning till than example 6～9.Comparative example 6～8 burns till under hydrogen/nitrogen atmosphere.The nitride phosphor that obtains in comparative example 6～8 conditions with visual inspection its luminosity for extremely low.Comparative example 9 burns till in hydrogen atmosphere, but luminous for not carrying out with visual inspection.When repeating this type of test, also can be to obtain identical test-results.
With formula M XSi Y(M contains the alkaline-earth metal be made up of the group of Ca, Sr, Ba, Zn more than at least 1 to NZ: Eu, and Z=2/3X+4/3Y) represented fluor, absorb the short wavelength of 250～450nm of visible region, and carry out strong reflection with the wavelength more than 450～500nm.Therefore, this fluor owing to the blueness that absorbs visible light, absorb glaucous short wavelength from blue, so carry out strong reflection in the wavelength side of green, yellow, redness etc.Utilize this characteristic, for example by and the combination of blue series LED, can have the character that obtains reddish white color system.
But above-mentioned fluor basis has creating conditions of the useful characteristics of luminescence or forms, and is understood its luminosity for lower.
Embodiment 7
Below, with reference to accompanying drawing embodiments of the present invention 7 are described.Wherein, embodiment 7 illustrations shown below light-emitting device in order to technological thought of the present invention is specialized, and that the present invention is not limited to light-emitting device is as follows.In addition, in order to offer some clarification on, and the size of each parts shown in the drawings or position are closed locating of exaggeration are also arranged.
Fluor used in the present invention contains the 1st fluor and when the variation of the surrounding temperature of fluor and the fluor of its change of luminous intensity and the 1st fluor the 2nd fluor about equally.And then under the condition that promptly changes because of surrounding temperature, contain change of luminous intensity and the 1st fluor the 2nd fluor about equally toward the variation fluor of the importing electric current of luminous element.Present embodiment 7 employed fluor particularly will carry out the 1st luminous fluor at the light that yellow to green area has a peak wavelength of luminescent spectrum and will carry out the 2nd luminous fluor at the light that red area has a peak wavelength of luminescent spectrum.The 1st fluor contains Y and Al, and contain be selected among Lu, Sc, La, Gd, Tb, Eu and the Sm at least one element and an element in Ga and In, and can to make the YA G that is activated with cerium be fluor.In addition, the 2nd fluor contains N, and contain be selected among Be, Mg, Ca, Sr, Ba and the Zn at least one element and at least one the element in C, Si, Ge, Sn, Ti, ZR and Hf, and/or can make the nitride phosphor that is activated with rare earth element.
The photodiode 200 of Figure 55 possesses the wire type photodiode of anchor leg 205 and inner lead 206, the cup portion of its anchor leg 205 is provided with L ED chip 202, and contain after the coating portion 201 of above-mentioned fluor led chip 202 can be covered state retrofilling in glass portion, constitute according to model assembly 204 resin mouldizations.Herein, the n lateral electrode of led chip 202 and p lateral electrode are used lead 203, and are connected to anchor leg 205 and inner lead 206.
In the photodiode that as above constitutes, the light luminous by luminous element (led chip) 202 is (hereinafter referred to as the part of " LED light ", to contain phosphor excitation in coating portion 201, and the fluorescence of the generation wavelength different, and the fluorescence that fluor produced and have neither part nor lot in exciting of fluor and the LED light colour mixture exported and exporting with LED light.
Generally speaking, because fluor is in the time of the rising of surrounding temperature, launching efficiency reduces, so autofluorescence body and the output of the light exported also reduces.In present embodiment 7, the reduction ratio of the luminous relatively output when surrounding temperature is 1 ℃ of variation is defined as luminous output reduced rate, and the luminous output reduced rate of the 1st fluor and the 2nd fluor is 4.0 * 10 -3[a.u./℃] below, be preferably 3.0 * 10 -3[a.u./℃] below, more preferably then be 2.0 * 10 -3[a.u./℃], be compared to prior art, then for more suppressing to produce the formation of the reduction of all light beams of light-emitting device [Im] because of heating.In addition, making is with respect to the luminous output reduced rate formation about equally of the temperature rising of the 1st fluor and above-mentioned the 2nd fluor.Also promptly, the poor of luminous output reduced rate of the 1st fluor and the 2nd fluor made 2.0 * 10 -3[a.u./℃] below, more preferably then make 2.0 * 10 -4[a.u./℃] below, and make luminous output reduced rate roughly the same.According to the measure of processing like this, the temperature profile that promptly can form the fluor that reduces because of the heating launching efficiency is roughly the same, even and surrounding temperature change and also can be with the light-emitting device of the generation that suppresses color shift.
Below, each formation that relates to embodiments of the present invention 7 is described in detail in detail.
[fluor]
Employed fluor in present embodiment 7 can use yttrium. and aluminium garnet is fluor and the light of redness can be carried out luminous fluor, particularly nitride phosphor combination person.This type of YAG is fluor and nitride, can mix and contains in coating portion 201, also can contain respectively in the coating portion 201 that is made of a plurality of layers.Below, describe its each fluor in detail.
(yttrium. aluminium. garnet is a fluor)
Present embodiment 7 employed yttriums. aluminium. garnet is fluor (YAG is a fluor), refer to contain Y and Al, and contain at least a element that is selected among Lu, Sc, La, Gd, Tb, Eu and the Sm and a kind of element in Ga and In, and the fluor that is activated with at least a element in rare earth element, and with from led chip 202 and luminous visible light or ultraviolet ray and be excited and luminous fluor.Particularly in present embodiment 7, also can utilize the different yttrium more than 2 kinds of composition that is activated with Ce or Pr. aluminum oxide is a fluor.Can enumerate as YAlO 3: Ce, Y 3Al 5O 12Y: Ce (YAG: Ce) or Y 4Al 2O 9: Ce, even this type of mixture.In addition, also can contain at least a of Ba, Sr, Mg, Ca, Zn, and then also can be suppressing the reaction of crystalline growth by containing Si, and the particle of fluorescent substance is reached unanimity.Herein, the YAG that is activated with Ce is that fluor is made the generalized explanation especially, use has the part of yttrium or is all replacing at least 1 the element that is selected from the group of being made up of Lu, Sc, La, Gd and Sm, or with the part of aluminium or all with the broad sense that fluor was comprised of the fluorescence of each or the two sides replacement of Ba, Tl, Ga, In.More specifically, with general formula (YGd 1-Z) 3Al 5O 12: the light light-emitting fluophor that Ce (but 0＜Z≤1) is represented or with general formula (Re 1-aSm a) 3Re ' 5O 12: the represented light light-emitting fluophor of Ce (Re ' is for being selected from least a among Al, Ga, the In for but 0≤a＜1,0≤b＜1, at least a in Y, Gd, La, Sc of Re).
Will be by using nitride-based compound semiconductor at the light-emitting element of luminescent layer and the light of luminous blueness and owing to absorb blue light, so the object colour is from the xanchromatic fluor and luminous green and red light or the light colour mixture more green and red than xanchromatic light when showing, the white color system illuminant colour that promptly can expect shows.Light-emitting device is in order to produce this colour mixture, serves as preferred the powder of fluor or volume are contained in the inorganics of the various resins of Resins, epoxy, acrylic resin or silicone resin etc. or silicon oxide, aluminum oxide etc.Contain such fluor, can be used for various uses such as the point-like that forms according to the degree ground thinning that sees through from the light of led chip or stratiform.According to the ratio of adjusting various fluor and resin etc. or coating, fill-up and the measure of selecting the emission wavelength of luminous element, promptly can provide tone arbitrarily such as the bulb look that contains adularescent.
In addition, according to the measure that light disposes the fluor more than 2 kinds successively of injecting from each luminous element, promptly can make can luminous effectively light-emitting device.Also be, by having on the luminous element of reflection part, be layered in long wavelength side and have absorbing wavelength, and contain the look transform component of fluor that can be luminous and long wavelength side has absorbing wavelength comparing more with it the long wavelength, and can carry out luminous look transform component etc. long wavelength more, promptly can effectively utilize reflected light.
When using YAG to be fluor, as radiation illumination and and (Ee)=0.1W.cm -2Above 1000W.cm -2Following led chip connects or closely connects and when disposing, also can be with the light-emitting device of making high-level efficiency and having sufficient anti-opticity.
Use is at the yttrium that is activated with cerium of present embodiment 7. and aluminum oxide is that the carried out green of fluor is that luminous YAG is a fluor, because garnet structure, so heat, light and moisture content are strong, and excite the peak wavelength of absorption spectrum to make near the 420nm to 470nm.In addition, peak luminous wavelength λ p also near 510nm, and have extend the flap down broad luminescent spectrum near 700nm.On the other hand, the yttrium that is activated with cerium. aluminum oxide is that the luminous YAG of the carried out red colour system of fluor is a fluor, also is garnet structure, and heat, light and moisture content are strong, and excites the peak wavelength of absorption spectrum to make near the 420nm to 470nm.In addition, peak luminous wavelength λ p near 600nm, and have extend the flap down broad luminescent spectrum near 750nm.
YAG with garnet structure is in the composition of fluor, and by replacing the part of Al with Ga, and luminescent spectrum is shifted in short wavelength side, and in addition, by a part of replacing the Y of composition with Gd and/or La, and luminescent spectrum is shifted in long wavelength side.Such YAG is a fluor, also can burn till by the raw material of for example the replacement element that can add surplus according to stoichiometric ratio being adjusted to obtain.Being converted to less than 2 one-tenth bigger and red compositions of green composition of Y is less.In addition, the brightness of 8 one-tenth above red composition increases reduces hastily.In addition, relate to and excite absorption spectrum also in the same manner, by replace with Ga the YAG with garnet structure be fluor composition in, the part of Al, and excite absorption spectrum to be shifted in short wavelength side, in addition, by replacing the part of the Y of composition, and excite absorption spectrum to be shifted in long wavelength side with Gd and/or La.YAG is the peak wavelength that excites absorption spectrum of fluor, more is positioned at short wavelength side for preferred than the peak wavelength of the luminescent spectrum of luminous element.When so constituting, to import when the electric current of luminous element increases, since the peak wavelength of the roughly consistent luminescent spectrum at luminous element of the peak wavelength that excites absorption spectrum, thus unlikely at the launching efficiency that reduces fluor, can form the light-emitting device of the generation that can suppress chroma offset.
Such fluor is as the raw material of Y, Gd, Ce, La, Al, Sm and Ga and use oxide compound, or high temperature and be easy to form the compound of oxide compound, and with stoichiometric ratio this type of mixed fully and obtain raw material.Or will be with stoichiometric ratio the rare earth element of Y, Gd, Ce, La, Sm be dissolved in the lysate of acid, it is burnt till with the coprecipitated material of oxalic acid and the coprecipitated oxide compound and the aluminum oxide that obtain, gallium oxide mixes and obtain mixing raw material.To this as fusing assistant and in right amount with the fluorochemical or the NH of ammonium fluoride etc. 4Cl mixes and is fills up in the crucible, and 1350～1450 ℃ temperature range was burnt till 2～5 hours and obtained to burn till product in air, and then in water, the product that will burn till grind and via clean, separation, drying, obtain by sieve at last.In addition, the manufacture method of the fluor of other embodiment 7, the two-stage of being formed with the 1st firing process that carries out in atmosphere or in the weakly reducing atmosphere and second firing process that in reducing atmosphere, carries out, the mixing raw material of the raw material of mixing phosphor and mixture that fusing assistant is formed are burnt till to preferably.Herein, weakly reducing atmosphere refers in the reaction process of the fluor that is formed expectation by mixing raw material, the weakly reducing atmosphere that can contain the state of necessary oxygen amount at least and set, by carrying out first firing process till the structure of the fluor that finishes expectation in this weakly reducing atmosphere forms, promptly can prevent the blackening of fluor, and can prevent the reduction of the assimilated efficiency of light.In addition, the reducing atmosphere of second firing process is meant the reducing atmosphere stronger than weakly reducing atmosphere.In when burning till with such two-stage, promptly can obtain the higher fluor of assimilated efficiency of excitation wavelength.Therefore, with so and the fluor that forms and when forming light-emitting device, promptly can be reduced to and obtain the necessary fluorescence scale of construction of tone of expectation, and can form light and take out the higher light-emitting device of efficient.
The yttrium that is activated to form the different ceriums more than 2 kinds. aluminum oxide is a fluor, can mix and uses, and also can distinguish independence and disposes.When respectively fluor independently being disposed, be easy to the fluor that photoabsorption is luminous according to self-emission device in the shorter wavelength side, comparing arranged in order that long wavelength side more is easy to absorb luminous fluor with it for preferred, can absorb effectively thus with luminous.
In present embodiment 7, when using YAG to be fluor, can use for example following composition as the 1st fluor.
Fluor 7-1:(Y0.90Gd0.10) 2.85Ce0.15Al5O12,
Fluor 7-2:(Y0.395Gd0.605) 2.85Ce0.15Al15O12,
Fluor 7-3:Y2.965Ce0.035 (Al0.8Ga0.2) 5O12,
Fluor 7-4:(Y0.8Gd0.2) 2.965Ce0.035Al5O12,
Fluor 7-5:Y2.965Ce0.035 (Al0.5Ga0.5) 5O12,
Fluor 7-6:Y2.85Ce0.15Al5O12.
Also have, YAG of the present invention is a fluor, is not limited to this type of.
Illustrate in greater detail with reference to Figure 92～97 and to relate to fluor 7-1～7-6.The figure of the luminescent spectrum when Figure 92 represents that with EX=460nm the YAG of fluor 7-1～7-4 is phosphor excitation.Figure 93 represents that the YAG of fluor 7-1～7-4 is the figure of the reflection spectrum of fluor.Figure 94 represents that the YAG of fluor 7-1～7-4 is the figure of the excitation spectrum of fluor.The figure of the luminescent spectrum when Figure 97 represents that with EX=460nm the YAG of fluor 7-5 and fluor 7-6 is phosphor excitation.Figure 95 represents that the YAG of fluor 7-5 is the figure of the excitation spectrum of fluor.Figure 96 represents that the YAG of fluor 7-6 is the figure of the excitation spectrum of fluor.
The YAG of this type of fluor 7-1～7-6 is a fluor, because its luminescence peak crest is different, so selected YAG with tone of expectation is a fluor.Then, self-excitation spectrum and reflection spectrum and selected luminous element.For example 1 YAG is that the peak wavelength of phosphor excitation spectrographic long wavelength side is about 456nm.When consideration promptly is passed to the situation of short wavelength side because of the increase luminous element that imports electric current, then be selected in the luminous element that has peak luminous wavelength than the long wavelength side of the long 5～10nm degree of this 456nm.In addition, also consider the excitation spectrum of the 2nd fluor and select luminous element.
On the other hand, as the 2nd fluor, and selected carry out when selected again YAG is fluor, considering following point after the luminous fluor with certain wavelength.For example, according to the pass of the 2nd fluor and luminous element, when the importing electric current was low, the luminous element of peak luminous wavelength as 457nm used in the driving that fixes of 20mA.When the YAG of selected fluor 7-6 was fluor, the YAG of fluor 7-6 was that the peak wavelength of the excitation spectrum of fluor is 457nm.Therefore, be when hanging down toward the importing current density of luminous element, it is luminous that the YAG of this fluor 7-6 is that fluor carries out most effectively.But, because the increase of the importing electric current of past this luminous element, and the peak wavelength of the luminescent spectrum of this luminous element is passed to short wavelength side 10nm degree.Peak luminous wavelength when being passed to 10nm degree short wavelength side since the YAG of fluor 7-6 be the launching efficiency of fluor for reducing, also reduce so YAG is the relative luminous intensity of fluor.Also promptly, to the relative reduction of ratio of the luminous luminous intensity after the conversion of exciting light.Therefore, using the YAG of fluor 7-6 is the light-emitting device of fluor, because of the increase of the importing electric current of past luminous element produces the situation of hue shift.With respect to this, when the YAG of selected fluor 7-5 was fluor, the peak wavelength of excitation spectrum was 440nm.Owing to increase importing electric current toward luminous element, and the YAG of fluor 7-5 to be the luminous intensity of fluor promptly improve.On the other hand, be that the luminous output of fluor reduces usually because of the heating of luminous element makes YAG.Therefore, using the YAG of fluor 7-5 is the light-emitting device of fluor, even owing to increase the importing electric current of past luminous element, and Yin Re and the hue shift that produces and the hue shift that produced because of the increase optical frequency skew of the current density of luminous element are for offseting, so can provide hue shift less, and have stable luminous light-emitting device.Therefore, use identically with peak wavelength when the 1st fluor increases the importing electric current of luminous element, or when the YAG that short wavelength side has a peak wavelength of excitation spectrum was fluor, its color harmony change of luminous intensity was few.Outside the above-mentioned fluor, can use various YAG is fluor.
(nitride phosphor)
In present embodiment 7, nitride phosphor absorbs the part of the luminous blue light by led chip 202 and carries out the light in yellow to red zone luminous.Providing a kind of is that fluor has the light-emitting device of above-mentioned formation simultaneously with nitride phosphor and YAG, by will be, and carry out the white luminous light-emitting device of warm colour system by the yellow of luminous blue light of led chip 202 and nitride phosphor to the red light colour mixture.The outer fluor that increases of nitride phosphor contains the yttrium that is activated with cerium. and aluminum oxide is that fluorescent substance serves as preferred.This is because by containing above-mentioned yttrium. aluminum oxide is a fluorescent substance, promptly can be adjusted to the cause of the colourity of expectation.The yttrium that is activated with cerium. aluminum oxide is a fluorescent substance, and a part that absorbs the blueness system luminous by led chip 202 is carried out light luminous of yellow area.Herein, according to blueness system and the yttrium luminous by led chip 202. aluminum oxide is that the colour mixture of the sodium yellow of fluorescent substance is carried out the luminous of the white white color system of indigo plant.Therefore, by with this yttrium. aluminum oxide is that the luminous fluor of fluorescent substance and red colour system is mixed together in the coating member 201 with light transmission, and and by led chip 202 luminous blueness system makes up, promptly can provide mixed light to carry out luminous light-emitting device with white color system.Preferred especially colourity is the light-emitting device that is positioned at the white color system on the track of blackbody radiation of chromaticity diagram.But, because the light-emitting device of the colour temperature of expectation is provided, and so also can suitably change yttrium. aluminum oxide is the fluorescence scale of construction and the luminous fluorescence scale of construction of red colour system of fluorescent substance.The mixed light of this white color system is carried out luminous light-emitting device, can reach the improvement that number R9 is estimated in special colour developing.
In the prior art, use the light-emitting device of the white color system of semiconductor element, the blueness of self-emission device system and be engaged in people's visual sense degree and adjust in the future from the green mean value of fluor to red light, and obtain by the colour mixture of this type of light.Usually, use the white color system tone of the light-emitting device of semiconductor light-emitting elements,, luminous mean value adjustment is obtained in the comparatively stable drive area that fixes of the output characteristic of light-emitting device.But this based light emitting device is LCD backlight, in the time of can carrying out the lighting source of light modulation, makes importing electric power, current density change and use.When prior art changed current density because of the output adjustment of light-emitting device, then luminous balance was destroyed, and produced hue shift, and reduced the quality of light source.Below describe embodiments of the present invention in detail.
At first, with reference to Figure 55.
Luminous element makes the peak wavelength of the luminescent spectrum with luminous element be passed to short wavelength side by increasing the importing electric current.This is when increasing input electric current, and then current density becomes big, and also improve the accurate position of energy.Therefore, become the big essential factor that waits according to obstacle therefrom.Toward the peak wavelength of the current density of luminous element luminescent spectrum hour with increase the change amplitude of the peak wavelength of the luminescent spectrum when importing electric current, when for example increasing the importing electric current of 20mA to 100mA in the present embodiment, be approximately the 10nm degree.
Use Figure 56 and Figure 57 and illustrate.
For example, using YAG as the 1st fluor is fluor.The YAG of fluor 3 is that phosphor excitation spectrographic peak wavelength is approximately 448nm.The luminous intensity of the peak wavelength 448nm of this excitation spectrum was made the luminous intensity 95 of 460nm at 100 o'clock.Therefore, be compared to when exciting YAG to be fluor with 460nm, the aspect when then exciting YAG to be fluor with 448nm has higher luminous intensity.The pass of luminous element and the 1st fluor probably is described by this situation.Import electric current luminous element just after, the peak luminous wavelength of selected luminous element is the luminous element of 460nm.This luminous element carries out blue-light-emitting.The YAG that is excited via the blue light of this luminous element is the green emitting that fluor carries out about 530nm.Then, increase the importing electric current of luminous element and import the electric current of 100mA.Increase the luminous output of semiconductor element therefrom, and increase luminous element and peripheral temperature with this situation.In addition, the peak luminous wavelength of luminous element is passed to the short wavelength side of 450nm from 460nm.This moment, YAG was that the peak wavelength that fluor is compared to excitation spectrum is 460nm, and then the luminous intensity of 450nm Side is for higher.Therefore, YAG be fluor to be compared to exciting light be 460nm, then 450nm Side shows high relatively luminosity.In addition, blue light 450nm than 460nm extremely visual sense efficient for lower.Therefore, because the blueness of luminous element system and YAG are that the green light brightness of fluor is for uprising, so to the relative intensity of the green light of blue light grow then.Therefore, the tone of light-emitting device only is passed to the green light side in the straight line that links blue light and green light.On the other hand, owing to increase and fluor reduces brightness, so the relative intensity of the green light of blue light is then died down according to surrounding temperature.Therefore, the tone of light-emitting device only is passed to the blue light side in the straight line that links blue light and green light.Balance according to this type of suppresses hue shift.
Use Figure 58 and Figure 59 and illustrate.
For example, use nitride phosphor as the 2nd fluor.The nitride phosphor of fluor 5 between 350nm to 500nm, the about 450nm of the peak wavelength of excitation spectrum.The luminous intensity of the peak wavelength 450nm of this excitation spectrum was made 100 o'clock, and the luminous intensity of 460nm is 95.Therefore, be compared to when exciting nitride phosphor with 460nm, the aspect when then exciting YAG to be fluor with 450nm has higher luminous intensity.The pass of luminous element and the 2nd fluor probably is described by this situation.When the importing current density of past luminous element was low, the peak luminous wavelength of selected luminous element was the luminous element of 460nm.This luminous element uses that the messenger is identical person when exciting the 1st fluor.It is luminous that this luminous element carries out blueness.The nitride phosphor that is excited via the blue light of this luminous element carries out the emitting red light of about 637nm.Then, increase the importing electric current of luminous element and import the electric current of 100mA.Increase the luminous output of semiconductor element therefrom, and increase luminous element and peripheral temperature with this situation.In addition, the peak luminous wavelength of luminous element is passed to the short wavelength side of 450nm from 460nm.At this moment, the peak wavelength that nitride phosphor is compared to excitation spectrum is 460nm, the luminous intensity height that then 450nm Side is relative.Therefore, nitride phosphor is compared to 460nm, and 450nm Side shows higher luminosity.In addition, blue light be 450nm than 460nm and its visual sense efficient for lower.Therefore, because the brightness of its red light of red light of the blue light of luminous element and nitride based fluor is for uprising, so to the relative intensity of the red colour system of blue light grow then.Therefore, the tone of light-emitting device is passed to the red light side a little in the straight line that links blue light and red light.On the other hand, owing to increase and fluor reduces brightness, so the relative intensity of the green light of blue light is then died down according to surrounding temperature.Therefore, the tone of light-emitting device is passed to the blue light side a little in the straight line that links blue light and red light.Balance according to this type of suppresses hue shift.
The relation of general explanation the 1st fluor and the 2nd fluor.Nitride phosphor not only comes the light of self-emission device, and also absorbing YAG is near the light of peak wavelength (approximately 530nm) of the luminescent spectrum of fluor, and excites.
And then in detail the mutual pass of above-mentioned luminous element and the 1st fluor and the 2nd fluor is described in detail.Produce heating by importing electric current in luminous element.According to the importing electric current that increases toward luminous element, and thermal value is increased.The major part of the heat that this luminous element produced is accumulated in coating member or fluor.Produce surrounding temperature therefrom and rise, and the reduction situation of the luminous output of fluor itself.With respect to this, by increasing the importing electric current toward luminous element, and make peak wavelength be passed to short wavelength side as the luminescent spectrum of above-mentioned luminous element, increase the luminous intensity of the 1st fluor.According to this type of interaction, and the 1st fluor can make the luminous output of color harmony change hardly and be maintained.In addition, the 2nd fluor also with the 1st fluor in the same manner, the luminous output of color harmony is changed hardly and be maintained.
Determine the tone of light-emitting device by each luminous interaction of above luminous element and the 1st fluor and the 2nd fluor.Also promptly, luminous element is along with the increase that imports electric current, and makes the peak wavelength of luminescent spectrum be passed to short wavelength side.With this situation, then the 1st fluor that is excited via this luminous element and the luminous intensity of the 2nd fluor also increase.On the other hand, along with increase toward the importing electric current of luminous element, and the luminous element heat of also setting out.According to this heating and its temperature is accumulated in the 1st fluor and the 2nd fluor or coating member etc.Make this type of fluor luminous be output as reduction according to this accumulation of heat.Therefore, even when increasing importing electric current toward luminous element, also can be to suppress the hue shift of light-emitting device.Selected according to the 1st fluor and the 2nd fluor, even then when light-emitting device produces the situation of hue shift, and also can with visually almost numbness to the situation of hue shift.When surveying the interaction of luminous element and the 1st fluor and the 2nd fluor, then the tone of light-emitting device is passed to direction that increases tone x and the direction that increases tone y.The offset direction of this tone is along the track of blackbody radiation and produce change.Along the color displacement of the track of blackbody radiation, vertically at the color displacement of the direction of the track of blackbody radiation, it is in people's vision, and the sensitivity of experiencing color displacement is for lower.In addition, according to the interaction (own absorption etc.) of the 1st fluor and the 2nd fluor, and the amplitude of color displacement is narrowed down.Therefore, the present invention can provide the light-emitting device that prevents hue shift.The present invention is easy to be subjected to the light-emitting device of the influence of temperature, and for example DC drives or import the semiconductor light-emitting apparatus, heat release difficulty of the bigger power train of electric power and accumulation of heat is easy to light-emitting device, or under drive environment, its effect is big especially.
Also have, luminous element is at the scope that is passed to short wavelength side because of the increase that imports electric power, the also fluor that can use excitation spectrum almost not change.For example, during the nitride phosphor of the fluor 5 of use embodiment, then in the scope of 420nm to 450nm, excitation spectrum does not almost change, but shows its effect by the combination with the YAG with feature of the present invention.In addition, have feature, and have the feature of excitation spectrum and luminous element as the temperature profile of above-mentioned fluor.When using other fluor beyond above-mentioned, also can be so that light-emitting device of the present invention to be provided.
In addition, also can consider the junction temperature of the thermoelectric resistance of light-emitting device or exothermic character, luminous element etc., and the position of the peak wavelength of excitation spectrum and luminous element is adjusted.
Embodiment 8
Followingly embodiments of the present invention 8 are described with reference to accompanying drawing.But, embodiment 8 illustrations shown below light-emitting device in order to technological thought of the present invention is specialized, the present invention is not limited to light-emitting device as follows.In addition, there is locating of exaggeration the size of each parts shown in the drawings or pass, position etc. in order to offer some clarification on.
Be used in fluor of the present invention, it is characterized in that, contain:
The 1st fluor, it is positioned on the luminous element of at least one; And
The 2nd fluor, its part of carrying out luminous light are to be absorbed in more than the 1st fluor at least a,
And the 1st fluor more is positioned at the luminous element side of at least one than the 2nd fluor.Particularly, the luminescent coating of present embodiment 8 has:
The 1st luminescent coating 303, it will carry out luminous at the light that red area has a peak wavelength of luminescent spectrum; And
The 2nd luminescent coating 306, it will carry out luminous at the light that yellow to green area has a peak wavelength of luminescent spectrum.The 1st luminescent coating 303 contains N, and contain be selected among Be, Mg, Ca, Sr, Ba and the Zn at least one element and be selected from least one element among C, Si, Ge, Sn, Ti, ZR and the Hf, and can contain with in rare earth element at least one element and the nitride phosphor that is activated.In addition, the 2nd luminescent coating 306 contains Y and Al, and contain be selected among Lu, Sc, La, Gd, Tb, Eu and the Sm at least one element and be selected from Ga and In in an element, and can to contain the YAG that is activated to be selected from least one element in the rare earth element be fluor.
Light-emitting device of the present invention has:
The 1st recess, it loads the 1st fluor and the luminous element of at least one; And
The 2nd recess, it contains the 1st recess, and loads the 2nd fluor and the luminous element of at least one.
Figure 74 is the sectional view of model utility of photodiode of the surface installing type of present embodiment 8.The 1st recess 301 and the 2nd recess are set in luminous inspection surface side on the encapsulation 308.Herein, the 1st recess 301 is arranged in the 2nd recess 305.
The 2nd fluor is on the luminous element of at least one, and/or with this on luminous element of different at least one of at least one luminous element.Also promptly shown in Figure 74, the light of blue region can be carried out luminous led chip 302 and be loaded in the 1st recess 301, and form the 1st luminescent coating 303 down with the state that can cover this led chip 302.And then the light of identical blue region can be carried out luminous led chip 304 and be loaded in the 2nd recess 305, and be formed with the 2nd luminescent coating 306 down with the state that can cover this led chip 304 and the 1st luminescent coating 303.When use has the model assembly of diffusant; cover the 1st luminescent coating 303 and the 2nd luminescent coating 306; and protect conducting wire 310, led chip and luminescent coating via outside atmosphere, also can be and the light of bright dipping is diffused in luminous inspection surface direction and carry out colour mixture with autofluorescence body layer.Herein, the n lateral electrode of led chip 302 and led chip 304 and p lateral electrode are used conducting wire 310 respectively and distinctly are connected the negative pole and the positive pole of the lead-in wire electrode 309 that is molded over encapsulation 308 by the gross.
In the photodiode that as above constitutes, the part of LED light excites the fluor that contains at the 1st luminescent coating 303, and the light of the red area of generation and LED light different wave length.In addition, the part of the LED light that produces because of led chip 304 and led chip 302 excite the fluor that contains at the 2nd luminescent coating 306, and the yellow area of generation and LED light different wave length is to the light of green area.From the 1st luminescent coating 303 and the 2nd luminescent coating 306 and the fluorescence and the helpless LED light of exporting exciting of fluor that produce carry out colour mixture, and the luminous observed ray of selfluminous device and exporting.Because so a plurality of led chips of use, and can directly excite a plurality of fluor according to each led chip, once with the light-emitting device in the past of several phosphor excitation, the present invention can make the light-emitting device that can carry out high brightness luminescent with the original luminescent spectrum of each fluor with a led chip so be compared to.
Like this be distinguished into the 1st luminescent coating and the 2nd luminescent coating or even the 3rd luminescent coating and when stacking gradually,, promptly can make the light-emitting device that can improve color developing by contain fluor respectively at each luminescent coating with the light bright dipping of different wavelength region may.Also be, because from containing and the peak wavelength of the luminescent spectrum of the red area of bright dipping exists in the scope of 600nm to 700nm at the red colour system fluor of the 1st luminescent coating, and contain at the YAG of the 2nd luminescent coating is the scope of the peak wavelength that excites absorption spectrum of fluor at 420nm to 470nm, so from the red colour system fluor and the light of bright dipping is that fluor absorbs by YAG hardly, and the utmost point carries out colour mixture with other the light of wavelength effectively.
In addition, the 1st recess 301 is formed on the depths partly from the 2nd recess 305.By such formation, carry out bright dipping and towards the light of the wavelength 500nm to 700nm of luminous inspection surface direction from the 2nd luminescent coating 306, because not had the red colour system fluor that excites absorption spectrum by the scope at wavelength 350nm to 600nm absorbs, so can make the light-emitting device that can improve color developing.
In addition, passing through like this is distinguished into 2 layers and forms luminescent coating, then from the 1st luminescent coating 303 and the light and the LED light of bright dipping, between through the 2nd luminescent coating 306, do not absorbed and spread by fluorophor particle, and the light of blue region, yellow to green area light and the auroral poles of red area for carrying out colour mixture effectively.Therefore, can improve selfluminous device and the color developing of the light of bright dipping.More preferably diffusant or pad are contained in the 2nd luminescent coating 306, or also can form diffusant or pad are contained model assembly on the 2nd luminescent coating 306.By taking such formation, promptly can more effectively carry out colour mixture.
Generally speaking, because fluor is when temperature rises around, its launching efficiency promptly reduces, so the output of the light of autofluorescence body and bright dipping also reduces.In present embodiment 8, it is that the light of the blue region of 460nm degree carries out under the state of luminous luminous element that fluor is coated in peak wavelength λ p, and the reduction ratio of surrounding temperature being carried out 1 ℃ of luminous relatively output when changing is called luminous output reduced rate.With respect to red colour system fluor and YAG is that the luminous output reduced rate that the temperature of fluor rises all makes 4.0 * 10 -3[a.u./℃] below, more preferably then make 2.0 * 10 -3Below [a.u./℃], compared with prior art, also can be to make the formation of the reduction that more can suppress all light beams [Im] of the light-emitting device that produces because of heating.In addition, can make with respect to red colour system fluor and YAG is the luminous output reduced rate formation about equally of the temperature rising of fluor.Also promptly, be the difference making 2.0 * 10 of the luminous output reduced rate of fluor with red colour system fluor and YAG -3[a.u./℃] below, more preferably then make 2.0 * 10 -4[a.u./℃] below, luminous output reduced rate can be made about equally.By processing like this, then the temperature profile of the fluor that reduces because of the heating launching efficiency is roughly the same, even and can form that surrounding temperature changes and also can be with the light-emitting device of the generation that suppresses chroma offset.
Below, each formation that relates to embodiments of the present invention 8 is described in detail in detail.
[fluor]
As fluor used in the present invention, the light of the different wavelength region may that is excited with ultraviolet to the light of visible region can be carried out luminous various fluor combinations and use.At this moment, penetrate the part of the light of light from the 1st fluor, select the fluor that is not absorbed respectively by the 2nd fluor.In present embodiment 8, also can use as fluor to be excited via UV-light and to produce the fluor of the light of promptly deciding color, can enumerate as concrete example, for example:
(1)Ca 10(PO 4)FCl∶Sb，Mn
(2) M 5(PO 4) 3Cl: Eu (but M is selected from least a among Sr, Ca, Ba, the Mg)
(3)BaMg 2Al 16O 27∶Eu
(4)BaMg 2Al 16O 27∶Eu、Mn
(5)3.5MgO.0.5MgF 2.GeO 2∶Mn
(6)Y 2O 2S∶Eu
(7)Mg 6As 2O 11∶Mn
(8)Sr 4Al 14O 25∶Eu
(9)(Zn、Cd)S∶Cu
(10)SrAl 2O 4∶Eu
(11)Ca 10(PO 4) 6ClB∶Mn、Eu
(12)Zn 2GeO 4∶Mn
(13) Gd 2O 2S: Eu and
(14)La 2O 2S∶Eu
Particularly, employed fluor in present embodiment 8 can use yttrium. aluminium. garnet (carbuncle type) fluor and the luminous red colour system fluor that can carry out red light, particularly nitride phosphor combination.This type of YAG is fluor and nitride phosphor, contains respectively in the luminescent coating that is made of a plurality of layers.Below, detailed description relates to each fluor.Herein, in the present invention, the particle diameter of fluor refers to the value that obtains via the volume reference size distribution curve, and above-mentioned volume reference size distribution curve is according to laser diffraction. the size-grade distribution that dispersion method is measured fluor obtains.Particularly, in the environment of 25 ℃ of temperature, humidity 70%, it is 0.05% hexamethylene sodium phosphate aqueous solution that fluor is dispersed in concentration, and by laser diffraction formula particle size distribution device (SALD-2000A), measures and obtains at particle size range 0.03 μ m～700 μ m.
(yttrium. aluminium. garnet is a fluor)
Use is at the yttrium of present embodiment 8. aluminium. and garnet is fluor (YAG is a fluor), be meant and contain Y and Al, and contain be selected among Lu, Sc, Lu, Gd, Tb, Eu and the Sm at least one element and be selected from Ga and In in an element, and be selected from the rare earth element at least one element and the fluor that is activated, and with from led chip 304 and luminous visible light or ultraviolet ray excited and carry out luminous fluor.Particularly in present embodiment 8, also utilizing the different yttrium more than 2 kinds that is activated with Ce or Pr. aluminum oxide is a fluor.From nitride-based compound semiconductor being used the light that carries out luminous blueness system at the luminous element of luminescent layer and when absorbing light colour mixture that blue light carries out the more green system of light of luminous green and red light or yellow system and red colour system from the object colour as the xanchromatic fluor and show, the white color system illuminant colour that promptly can expect shows.Light-emitting device is in order to produce this colour mixture, and the powder of fluor or volume (bulk) are contained in the light transmission inorganics of the various resins of Resins, epoxy, acrylic resin or silicone resin etc. or silicon oxide, aluminum oxide, silicon sol etc. for preferred.Like this contain fluor, can become to see through purposes such as figure point-like person that the degree from the light of led chip forms or stratiform person according to thinning and do various uses.According to tone arbitrarily such as the bulb look that the ratio of fluor and resin etc. or coating, fill-up is carried out various adjustment and select the measure of the emission wavelength of luminous element, promptly can provide containing adularescent.
In addition, by the light of injecting that comes self-emission device is respectively disposed fluor more than 2 kinds successively, carry out luminous light-emitting device effectively but promptly can make the utmost point.Also be, by having on the luminous element of reflection part, to contain and have absorbing wavelength at long wavelength side, and can carry out the colour switching parts of luminous fluor and compare more to have absorbing wavelength the long wavelength at long wavelength side with it, can carry out luminous colour switching stacking part etc. long wavelength more, promptly can effectively utilize reflected light.
When using YAG to be fluor, as radiation illumination and and (Ee)=0.1W.cm -2Above 1000W.cm -2Following led chip be connected or near and during configuration, also can be to make light-emitting device expeditiously with sufficient anti-opticity.
Use is at the yttrium that is activated with cerium of present embodiment 8. and aluminum oxide is that the carried out green of fluor is that luminous YAG is a fluor, because garnet structure, so strong, and excite the peak wavelength of absorption spectrum to be produced near the 420nm to 470nm to heat, light and moisture content.In addition, have and extend the broad luminescent spectrum of the flap down, its peak luminous wavelength λ p also near the 510nm till near the 700nm.On the other hand, the yttrium that is activated with cerium. aluminum oxide is that the luminous YAG of the carried out red colour system of fluor is that fluor also is a garnet structure, and it is strong to heat, light and moisture content, and excites the peak wavelength of absorption spectrum to make near the 420nm to 470nm.In addition, have and extend the broad luminescent spectrum of the flap down, its peak luminous wavelength λ p is near 600nm, till near the 750nm.
YAG with garnet structure be fluor composition in, by with Ga for the conversion Al a part, make luminescent spectrum be offset to short wavelength side, the part by replacing the Y of composition with Gd and/or La makes luminescent spectrum be offset to long wavelength side in addition.The replacement of Y is less than 2 one-tenth, and it forms the bigger and red composition less state of green composition.In addition, 8 one-tenth above brightness that increase red composition are reduction sharp.In addition, relate to and excite absorption spectrum also identical, YAG with garnet structure be fluor composition in, by replace the part of Al with Ga, make and excite absorption spectrum to be offset to short wavelength side, in addition, by a part of replacing the Y of composition, make to excite absorption spectrum to be offset to long wavelength side with Gd and/or La.YAG is the peak wavelength that excites absorption spectrum of fluor, more is positioned at short wavelength side for preferred than the peak wavelength of the luminescent spectrum of luminous element.When making such formation, when increasing the electric current that imports at luminous element, owing to excite the peak wavelength of absorption spectrum, roughly unanimity is at the peak wavelength of the luminescent spectrum of luminous element, do not have the launching efficiency that reduces fluor so can form, can suppress the luminous of generation of chroma offset and put.
Such fluor uses oxide compound or in temperature and be easy to form the compound of oxide compound and as the raw material of Y, Gd, Ce, La, Al, Sm and Ga, fully this type of mixing obtained raw material with stoichiometric ratio.Perhaps will be with oxalic acid will be with stoichiometric ratio, the lysate that the rare earth element of Y, Gd, Ce, La, Sm is dissolved in acid is coprecipitated, and it is burnt till and coprecipitated oxide compound and the aluminum oxide obtained, cerium oxide mixes and obtain mixing raw material.To this as fusing assistant and an amount of fluorochemical of mixed fluoride ammonia etc. and be fills up to crucible, 1350～1450 ℃ temperature range was burnt till 2～5 hours and was obtained to burn till product in air, then, the product that will burn till in water grind, and, obtain by sieve at last via clean, separation, drying.In addition, the manufacture method of the fluor of other embodiment, burn till with the following two-stage of being formed to preferably:
First firing process, it carries out the mixture that the mixing raw material and the fusing assistant of the raw material of mixing phosphor are formed in atmosphere or in the weakly reducing atmosphere; And
Second firing process, it carries out in reducing atmosphere.
Herein, weakly reducing atmosphere refers in the reaction process of the fluor that forms expectation from mixing raw material, the state that can contain the oxygen amount that is necessary at least descends and the weakly reducing atmosphere of setting, by in this weakly reducing atmosphere, carrying out first firing process, till the structure of the fluor of expecting forms end, the black change of fluor can be prevented, and the reduction of the assimilated efficiency of light can be prevented.In addition, the reducing atmosphere of second firing process refers to the reducing atmosphere stronger than weakly reducing atmosphere.When burning till like this, promptly can obtain the higher fluor of assimilated efficiency of excitation wavelength with the two-stage.Therefore, with so and the fluor that forms and when forming light-emitting device, promptly can lowering, and can form light and take out the higher light-emitting device of efficient for the necessary fluorescence scale of construction of the tone that obtains to expect.
The yttrium that is activated with the cerium more than 2 kinds of different compositions. aluminum oxide is a fluor, can mix and uses, and also can distinguish independence and disposes.During respectively independent and configuration fluor, be easy to absorb luminous fluor in shortwave wavelength side more, compare with it at long wavelength side and be easier to absorb the order of luminous fluor and be configured to preferred according to self-emission device.Can absorb effectively thus with luminous.
(nitride phosphor)
The 1st fluor used in the present invention, comprise N, and contain be selected among Be, Mg, Ca, Sr, Ba and the Zn at least one element and at least one the element in C, Si, Ge, Sn, Ti, ZR and Hf, and give nitride phosphor with at least one element in the rare earth class element.In addition, as the form 8 of this enforcement and the nitride phosphor that uses, by absorbing and luminous visible light, ultraviolet ray is excited and carries out luminous fluor from led chip.Fluor particularly of the present invention is added with Sr-Ca, Si-N:Eu, Ca-Si-N:Eu, Sr-Si-N:Eu, Sr-Ca-Si-O-N:Eu, Ca-Si-O-N:Eu, the Sr-Si-O-N:Eu silicon nitride of Mn.The basic comprising element of this fluor is with general formula L XSi YN (2/3X+4/3Y): Eu or L XSi YO ZN (2/3X+4/3Y-2/3Z): Eu (any one of LSr, Ca, Sr and Ca) is represented.In the general formula, X and Y serve as preferred with X=2, Y=5 or X=1, Y=7, but also can use arbitrarily.Particularly, the basic comprising element is added with the (Sr of Mn with use XCa 1-X) 2Si 5N 8: Eu, Sr 2Si 5N 8: Eu, Ca 2Si 5N 8: Eu, Sr XCa 1-XSi 7N 10: Eu, SrSi 7N 10: Eu, CaSi 7N 10: the represented fluor of Eu is preferred, but in the composition of this fluor, also can contain be selected from the group that Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and Ni form more than at least a kind.But the present invention is not limited at this embodiment 8 and embodiment.Any one of LSr, Ca, Sr and Ca.Sr and Ca can change proportioning according to expectation.
By Si being used composition, promptly can provide the fluor of cheapness and good crystallinity at fluor.
The europium Eu of rare earth class element is used at luminescence center, and europium is mainly the accurate position of the energy with divalent and 3 valencys.Fluor of the present invention uses Eu to the alkaline-earth metal silicon nitride of parent 2+And as activator.Eu 2+Be easy to oxidized, and with the Eu of 3 valencys 2O 3The participation of O is difficult for obtaining fluor preferably greatly.Therefore, use O from Eu 2O 3And remove in system's epigenesist is preferred.For example, it is preferred using europium monomer, nitrogenize europium.But, then do not have this restriction when adding Mn.
The Mn of additive promotes Eu 2+Diffusion, and can reach luminosity, the raising of the luminous efficiency of energy efficiency, quantum yield etc.Mn contains in raw material, or Mn monomer or Mn compound are contained in the manufacturing step expires, and all burns till with raw material.But Mn does not contain in the basic comprising element after burning till, even or contain and amount is only residual a small amount of more originally.This is to be regarded as in firing process, and Mn is the reason of dispersing.
Fluor in the basic comprising element, or and the basic comprising element all contain be selected from the group that Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, O and Ni form more than at least a kind.This type of element has the effect that increases particle diameter, raising luminosity etc.In addition, B, Al, Mg, Cr and Ni have the effect that can suppress twilight sunset.
Such nitride phosphor absorbs by led chip 302 and the part of luminous blueness system, and carries out the light in yellow to red zone luminous.With nitride phosphor and YAG is that fluor has the light-emitting device of above-mentioned formation simultaneously, and will be according to led chip 302,304 and luminous blueness system and YAG to be the light of fluor and yellow to the red light of nitride phosphor carry out colour mixture, promptly can make the light-emitting device that the mixed light with warm colour system carries out bright dipping.The yttrium that is activated with cerium. aluminum oxide is a fluorescent substance, absorbs by led chip 304 and the part of luminous blueness system, and carries out the light of yellow area luminous.Herein, luminous blueness system and yttrium by led chip 304. aluminum oxide is the sodium yellow of fluorescent substance, according to colour mixture and the blue white white of luminous one-tenth.Therefore, according to respectively that this red colour system is luminous fluor and yttrium. aluminum oxide is that fluorescent substance contains at the 1st luminescent coating and the 2nd luminescent coating, and will be according to led chip 302 or led chip 304 and the measure of luminous blueness system combination promptly can provide the mixed light with white color system to carry out luminous light-emitting device.Preferred especially person's colourity is the light-emitting device that is positioned at the white color system on the track of blackbody radiation of chromaticity diagram.But because the light-emitting device of the colour temperature of expectation is provided, and so also can be suitably to change yttrium. aluminum oxide is the fluorescence scale of construction and the luminous fluorescence scale of construction of red colour system of fluorescent substance.The mixed light of this white color system is carried out luminous light-emitting device, can reach the improvement that number R9 is estimated in special colour developing.Luminous one-tenth only is in the past blue based light-emitting device and the yttrium that is activated with cerium. aluminum oxide is the light-emitting device of white color system of the combination of fluorescent substance, in near colour temperature Tcp=4600K, special colour developing estimate number R9 for roughly near 0, and red composition is inadequate.Therefore, improve special colour developing and estimate number R9 formation solution problem, but according to using luminous fluor and the yttrium of red colour system among the present invention. aluminum oxide is the measure of fluorescent substance, promptly can improve special colour developing and estimate number R9.
Then, fluor ((Sr of the present invention is described XCa 1-X) 2Si 5N 8: manufacture method Eu), but be not limited to this manufacture method.Above-mentioned fluor contains Mn, O.
Sr, the Ca of raw material are pulverized.It is preferred that the Sr of raw material, Ca use monomer, but also can use the compound of imide compound, amide compound etc.In addition, raw material Sr, Ca also can contain B, Al, Cu, Mg, Mn, Al 2O 3Deng.Carry out the Sr of raw material, the pulverizing of Ca.The Sr, the Ca median size that obtain by pulverizing are approximately 0.1 μ m to 15 μ m for preferred, but are not limited to this scope.The purity 2N of Sr, Ca is above to be preferred, but is not limited to this.Owing to more improve admixture, thus also can with metal Ca, metal Sr, metal Eu make alloy state at least 1 or more after, carry out nitrogenize, pulverize and use as raw material afterwards.
The Si of raw material is pulverized.It is preferred that the Si of raw material uses monomer, but also can use nitride-based compound, imide compound, amide compound etc.Si for example 3N 4, Si (NH 2) 2, Mg 2Si etc.The purity 3N of the Si of raw material is above to be preferred, but also can contain Al 2O 3, Mg, metal boride (Co 3B, Ni 3B, CrB), manganese oxide, H 3BO 3, B 2O 3, Cu 2Compound such as O, CuO.Silicon is also pulverized in the same manner with Sr, the Ca of raw material.About 0.1 μ m to the 15 μ m of the median size of Si compound is preferred.
Then, in nitrogen atmosphere, Sr, the Ca of raw material carried out nitrogenize.Respectively this reaction formula is shown in following formula 16 and formula 17.
(formula 16)
(formula 17)
In nitrogen atmosphere, with 600～900 ℃ with the about nitrogenize of Sr, Ca 5 hours.Sr, Ca also can mix and carry out nitrogenize, also can each carry out nitrogenize respectively.Can obtain the nitride of Sr, Ca thus.The nitride of Sr, Ca is highly purified to be preferred, but also can use commercially available.
In nitrogen atmosphere, the Si of raw material is carried out nitrogenize.This reaction formula is shown in following formula 18.
(formula 18)
Silicon Si is also in nitrogen atmosphere, with 800～1200 ℃ of about nitrogenize 5 hours.Obtain silicon nitride therefrom.Silicon nitride used in the present invention, highly purified is preferred, but also can use commercially available.
The nitride of Sr, Ca or Sr-Ca is pulverized.Carry out the pulverizing of the nitride of Sr, Ca, Sr-Ca.
In the same manner, the nitride of Si is pulverized.In addition, in the same manner with the compd E u of Eu 2O 3Pulverize.Use europium sesquioxide and as the compound of Eu, but also can use metal europium, nitrogenize europium etc.In addition, the Z of raw material also can use imide compound, amide compound.Europium sesquioxide is highly purified to be preferred, but also can use commercially available.The median size of the nitride of the alkaline-earth metal after the pulverizing, silicon nitride and europium sesquioxide, 0.1 μ m to 15 μ m is preferred.
In above-mentioned raw materials, also can contain be selected from the group of forming in Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, O and Ni Europe more than at least a kind.In addition, also can be in following mixed processes, regulate use level and the above-mentioned element of Mg, Zn, B etc. is mixed.This type of compound also can be added in the raw material separately, but adds with the form of compound usually.This kind compound has H 3BO 3, Cu 2O 3, MgCl 2, MgO.CaO, Al 2O 3, metal boride (CrB, Mg 3B 2, AlB 2, MnB), B 2O 3, Cu 2O, CuO etc.
After carrying out above-mentioned pulverizing, with the nitride of Sr, Ca, Sr-Ca, the nitride of Si, the compd E u of Eu 2O 3Mixture burn till.Can obtain to be added with (the Sr of Mn by burning till XCa 1-X) 2Si 5N 8: Eu and the fluor represented.To be expressed as follows by the reaction formula of this basic comprising element that burns till.
(formula 9)
Wherein, the cooperation ratio according to each raw material of change promptly can change the composition as the fluor of purpose.
Firing temperature can burn till 1200 to 1700 ℃ scope, but serves as preferred with 1400 to 1700 ℃ firing temperature.Burning till use heats up lentamente, and carry out stage that a few hours burn till with 1200 to 1500 ℃ and burn till to preferably, carry out burning till of fs but also can use with 800 to 1000 ℃, and heating and carry out the two-stage that subordinate phase burns till with 1200 to 1500 ℃ and burn till (multistage burns till) lentamente.The raw material of fluor uses the crucible, boat of boron nitride (BN) material and burns till to preferably.Outside the crucible of boron nitride material, also can use aluminum oxide (Al 2O 3) crucible of material.
Manufacture method according to using as above promptly can obtain the fluor as purpose.
In an embodiment of the present invention, use nitride phosphor especially and as reddish light being carried out luminous fluor, but in the present invention, also can make the luminescent coating 303 that contains the red colour system fluor beyond the nitride phosphor.The light of such redness can be carried out luminous fluor, be that the light of 400～600nm is excited and carries out luminous fluor by wavelength, can enumerate as Y 2O 2S:Eu, La 2O 2S:Eu, CaS:Eu, SrS:Eu, ZnS:Mn, ZnCdS:Ag, Al, ZnCdS:Cu, Al etc.According to being the luminescent coating of fluor and the measure that contains the luminescent coating combination that the light of redness can be carried out luminous fluor, promptly can improve the color developing of light-emitting device with such YAG that contains.
[led chip 302,304]
Can utilize the various light sources that can excite the 1st fluor and the 2nd fluor and as the excitation light source of fluor of the present invention.Can enumerate semiconductor light-emitting elements as the led chip representative, semiconductor Laser device etc.Particularly in present embodiment 8, excite the luminous element led chip 302 and the led chip 304 of the light source of the 1st fluor and the 2nd fluor.Or as other embodiment of the present invention, the light that also combination can be able to be carried out the luminous element of luminescence-utraviolet and will absorb this ultraviolet ray and have different wavelength carries out luminous fluor and the light source that forms, as the light source that excites the 1st fluor and the 2nd fluor.For example, to carry out the led chip of luminescence-utraviolet and absorb this ultraviolet ray and carry out blue region light luminous fluor combination and as excitation light source, and form the survey of self-excitation light source and dispose the 1st luminous fluor of the light that excites this excitation light source and carry out red area successively and excite this excitation light source and carry out the light-emitting device of the 2nd luminous fluor of green light to yellow area.According to making such formation, owing to from the 2nd fluor and the light of bright dipping is absorbed by the 1st fluor, form the light-emitting device that can improve color developing so can utilize the led chip that carries out luminescence-utraviolet.
As present embodiment 8, with the 1st fluor, the 2nd fluor and luminous element combination, and the light of making the wavelength conversion that will be undertaken by the fluor that excites this type of carries out colour mixture and during the light-emitting device of bright dipping, the led chip that then uses the light of the wavelength that can excite this fluor to carry out bright dipping.Led chip according to mocvd method etc. and on substrate, form GaAs, InP, GaAlAs, InGaAlP, InN, AlN, GaN, InGaN, AlGaN, InGaAIN etc. semi-conductor and as luminescent layer.Can enumerate as having same sex structure, heterojunction structure or two heterogeneous constitutor of MIS joint, PIN joint or PN joint etc. as semiconductor structure.Material or this mixed crystal degree by semiconductor layer can carry out various selections with emission wavelength.In addition, also the semiconductor active layer can be made single quantum well structure or the multiple quantum trap structure that is formed on the film that produces the quantum effect.Can be effectively on preferred the effective shorter wavelength of excited fluorescent body be carried out luminous nitride-based compound semiconductor (general formula I n iGa jAl KN, wherein, 0≤i, 0≤j, 0≤k, i+j+k=1).
When using gallium nitride compound semiconductor, be fit to use the material of sapphire, spinel, SiC, Si, ZnO, GaN etc. at semiconductor substrate.In order to form the gan of good crystallinity, use sapphire substrate more preferred.When growing up semiconductor film on sapphire substrate,, and form gallium nitride semiconductor thereon with PN joint with the buffer layer of formation GaN, AlN etc.In addition, also can be with SiO 2Being chosen to long GaN monocrystalline itself as shielding on sapphire substrate utilizes as substrate.During this situation, the also mode that can remove according to etching and with SiO after the form of each semiconductor layer 2Be separated into luminous element and sapphire substrate.Gallium nitride compound semiconductor shows N type electroconductibility under the state of impurity not.When form improving the n type gallium nitride semi-conductor of expectations such as luminous efficiency, suitably import Si, Ge, Se, Te, C etc. and as N type hotchpotch for preferred.On the other hand, when forming P type gallium nitride semiconductor, be doped with Zn, Mg, Be, Ca, Sr, the Ba etc. of P type hotchpotch.
Gallium nitride compound semiconductor only is doped with P type hotchpotch, thus be difficult to carry out the P typeization, so after P type hotchpotch imports, carry out the P type and turn to preferably by carry out anneal according to heating, low-velocity electron radiation exposure or the irradiation of electricity slurry etc. of stove.Layer as concrete luminous element constitutes, enumerate as on sapphire substrate or silicon carbide the semi-conductive N type of stacked n type gallium nitride contact layer, aluminium nitride with the buffer layer that forms gan, aluminium nitride etc. with low temperature. the P type contact layer of the semi-conductive N type of gallium coating, the semi-conductive active coating of InGaN that is doped with Zn and Si, the semi-conductive P type of aluminium gallium nitride alloy coating, gallium nitride semiconductor.When having the led chip 302 of sapphire substrate in order to form led chip 302, form exposing after the face of P-type semiconductor and N-type semiconductor according to modes such as etchings, use sputtering method or vacuum vapour deposition etc. can form each electrode of shape of expectation on semiconductor layer.During the situation of SiC substrate, also can utilize the electroconductibility of substrate itself and form a pair of electrode.
Then, have the patterning method of band of adamantine point of a knife according to rotation and directly that formed semiconductor crystal wafer etc. is complete disconnected, or incision is than point of a knife wide cut more (hemisection) after the ditch of wide cut, the cutting semiconductor wafer by external force.Perhaps, for carrying out straight-line line back and forth, and for example on semiconductor crystal wafer, superfine straight line (warp) is directed to after the checkerboard according to the diamond needle of leading portion, the cutting crystal wafer by external force, and cut into shaped like chips from semiconductor crystal wafer.So processing promptly can form the led chip 302 of nitride-based compound semiconductor.
In the luminous light-emitting device of the present invention, consider the absorbing wavelength that excites of fluor at excited fluophor, and the peak luminous wavelength of led chip can be made below the above 530nm of 350nm.
In addition, according to making the luminous output that to control led chip 302 and led chip 304 respectively, and control carries out wavelength conversion according to the 1st fluor and the 2nd fluor and the measure of the colour mixture state of the light of bright dipping, also can make the light-emitting device that can be selected from by the colour temperature of regulating mixed light.
[conducting wire-310]
Be needed as and the resistive of the electrode of led chip, the good person of connectivity, electrical conductivity and heat conductivity of machinery as conducting wire 310.As thermal conduction degree 0.01cal/ (s) (cm 2) (℃/cm) above be preferably, more preferably then be 0.5cal/ (s) (cm 2) (℃/cm) more than.In addition, consider operation etc. and its more preferably the diameter of conducting wire be more than the Φ 10 μ m, below the Φ 45 μ m.Particularly in the coating portion of containing fluor with do not contain the interface of the model assembly of fluor, its conducting wire is easy to broken string.Use identical materials respectively and import fluor, consider because the thermal expansion amount of essence is different, so be easy to broken string.Therefore, the diameter 25 μ m of conducting wire are above to be preferred, and the viewpoint of luminous area or processing easness, then 35 μ m are following is preferred.
Particularly, can enumerate as the metal that uses gold, copper, platinum, aluminium etc. and the conducting wire of this type of alloy as such conducting wire.Such conducting wire can cohere electrode, inner lead and the anchor leg etc. that machine is connected each led chip by lead easily.
[encapsulation 308]
Originally execute the encapsulation 308 of form 8, have the 1st recess 301 that loads led chip 302 and the 1st luminescent coating 303 and contain the 1st recess, and load the 2nd recess of LED304 and the 2nd luminescent coating 306.In addition, supply of electric power is molded into by the gross the part of encapsulation at the positive and negative a pair of lead-in wire electrode 309 of led chip.Shown in Figure 74, the 1st recess 301 is by the bottom surface of the 2nd recess 305 that is mounted with led chip 304, and forms preferred reaching the direction opposite with luminous inspection surface deeply.Perhaps, also can in the 2nd recess 305, be mounted with the 1st recess that cup-shaped is set on the identical bottom surface of led chip 304.In addition, other embodiment intermediary spacer and led chip 304 is loaded on the same one side that is mounted with led chip 302, and led chip 302 by led chip 304 only thickness part of spacer be loaded near processing in the recess bottom surface.And then,, according to the roller shutter printing or use the coating method of spraying plating mode to form after the 1st luminescent coating 303, be loaded in the recess bottom surface and get final product the luminous inspection surface side surface of led chip 302 at other embodiment.By processing as above, promptly can positively only cover the led chip 302 of expectation with the formation material of the luminescent coating that contains the red colour system fluor.In addition, from containing at the fluor of the 2nd luminescent coating 306 and bright dipping and towards the light of luminous inspection surface direction, the red colour system fluor that is not contained in the 1st luminescent coating absorbs, so can make the light-emitting device that can improve color developing.
Such encapsulation 308 can form more simply according to mode moulding, insertion moulding etc.Can use as the thermoplastically material of encapsulation that aromatic nylon is a resin, (PPA), Sulfone is the thermoplastic resin of resin, polyamide-imide resin (PAI), polyketone resin (PK), polycarbonate resin, polyphenylene thioether sulfide (PPS), liquid crystalline polymers (LCP), ABS resin, PBT resin etc. etc. to poly-butyramide resin.Also have, also the person of containing the glass fibre can be used this type of thermoplastic resin and as the thermoplastically material.By such glass fibre that contains, can form and have high rigidity and high-intensity encapsulation.Herein, the 1st recess and the 2nd recess can form according to the mode of global formation when using the encapsulated moulding of forming model.
In addition, encapsulation also can form to use metallic substance.During this situation, recess can form easily according to imposing press process, lead-in wire electrode intermediary's insulativity parts and be formed on the part of encapsulation.Passing through like this used metallic substance as packaged material measure promptly can be made the light-emitting device that can improve exothermicity.
Bonding in the encapsulation recess of led chip can be undertaken by the insulativity caking agent of heat-curing resin etc.Particularly, can enumerate as Resins, epoxy, acrylic resin or imide resin etc.In addition, for according to the down mode of subtend, and reach electric property conducting, can use Ag paste, carbon paste agent, metal coupling, eutectic frequency band etc. the electrode surface and the lead-in wire electrode of led chip at the installation method that connects of lead-in wire electrode.And then in order to improve the light utilising efficiency of photodiode, also can will dispose the surface of anchor leg of led chip make mirror-like, and have the reflection merit on its surface passable.The above 0.8S of surperficial granularity 0.1S during this situation is following to be preferred.
[lead-in wire electrode 309]
As the positive and negative a pair of lead-in wire electrode that uses in present embodiment 8, with supply of electric power at led chip, and according in demand and intermediary's insulativity parts are formed on the part of encapsulation 308.As other embodiment, to the lead-in wire electrode of positive and negative any one party, the 1st recess and the 2nd recess are set directly, also can intermediary's insulativity caking agent and load led chip.As the concrete resistance of lead-in wire electrode, serving as preferred below 300 μ Ω-cm.More preferably then be below 3 μ Ω-cm.In addition, when being loaded in a plurality of led chips on the lead-in wire electrode, since many from the heating quantitative change of led chip, so can try to achieve thermal conduction degree preferably.Particularly, with 0.01cal/ (s) (cm 2) (℃/cm) above be preferably, more preferably then be 0.5cal/ (s) (cm 2) (℃/cm) more than.Enumerate as iron, copper, ferruginous copper, stanniferous copper the pottery of additional plated design etc. as the material that satisfies this type of condition.
[anchor leg 402]
As the anchor leg 402 of present embodiment 8, have the led chip 302 of configuration shown in Figure 76 and the 1st recess 301 and the 2nd recess of led chip, to carrying out stow, have abundant size and get final product by cutting machine etc.Shown in Figure 76, the 1st recess 301 is formed on the direction opposite with luminous inspection surface more deeply for preferred by the bottom surface of the 2nd recess 305 that is mounted with led chip 304.Perhaps, also can in the 2nd recess 305, be mounted with on the same bottom surface of led chip 304, the 1st recess of cup-shaped is set.In addition,, also can be mounted with on the same one side of led chip 302 at other embodiment, intermediary's spacer and load led chip 304, and led chip 302 according to led chip 304 and only the thickness of spacer can be loaded in position near the recess bottom surface.And then at other embodiment, also can be with luminous inspection surface side surface to led chip 302, according to the roller shutter printing or use the coating method of spraying plating mode to form after the 1st fluorescent layer 303, be loaded on the recess bottom surface.According to processing as above, promptly can positively only cover the led chip 302 of expectation with the formation material of the luminescent coating that contains the red colour system fluor.In addition, a plurality of led chips are being set, and with anchor leg as the common electrode of led chip and when utilizing, be required to have the connectivity of sufficient electrical conductivity and wire bonds etc.
The cup of led chip 302,304 and anchor leg 402 bonding can be undertaken by heat-curing resin etc.Particularly, can enumerate as Resins, epoxy, acrylic resin or imide resin etc.In addition, for according to ventricumbent led chip etc. and and anchor leg is bonding all can be electrically connected, can use Ag paste, carbon paste agent, metal coupling etc.And then in order to improve the light utilising efficiency of photodiode, also can will dispose the surface of anchor leg of led chip make mirror-like, and have the reflection merit on its surface passable.Surface roughness 0.1S during this situation is above to be preferred below 0.8.In addition, as the concrete resistance of anchor leg, 300 μ Ω-cm are preferred, more preferably then are below 3 μ Ω-cm.In addition, long-pending when putting a plurality of led chip on anchor leg, because many, so can be in the hope of thermal conduction degree preferably from the heating quantitative change of led chip.Particularly, with 0.01cal/ (s) (cm 2) (℃/cm) above be preferably, more preferably then be 0.5cal/ (s) (cm 2) (℃/cm) more than.Can enumerate as iron, copper, ferruginous copper, stanniferous copper, add the pottery of plated design etc. as the material that satisfies this type of condition.When using such metal, the processing that the 1st recess and the 2nd recess can be by the forming mould types, press process etc. form.
[inner lead 401]
As inner lead 401, can reach be configured in anchor leg 402 on being connected of the conducting wire 310 that is connected of led chip 302.When being arranged on a plurality of led chips on the anchor leg, then must making can be configured to each conducting wire between contactless formation.Particularly, along with separating from anchor leg, the area of the lead jointing end face by increasing inner lead then, then can prevent with from anchor leg and the contacting of the conducting wire that isolating inner lead is connected.With the rugosity that is connected end face of conducting wire, consider close property and serving as preferred below the above 10S of 1.6S.For the leading section of inner lead is formed different shape, the shape and the boring of the news frame that can determine with the type frame in advance to go between and forming, or also can after forming whole inner leads, form by a part that eliminates inner lead top.And then also can be after inner lead boring is formed, according to the measure of pressurizeing, and form the area and the end face height of the end face of expectation simultaneously from the end face direction.
Inner lead is required to have preferably the connectivity and the electrical conductivity of wire bonds with conducting wire etc.To serve as preferred below 300 μ Ω-cm, more preferably then is below 3 μ Ω-cm as concrete resistance.As the material of the condition that satisfies this type of, can enumerate as iron, copper, ferruginous copper, stanniferous copper and be coated with aluminium, iron, copper of copper, gold and silver etc.
[luminescent coating 303,306]
The 1st luminescent coating 303 of present embodiment 8 and the 2nd luminescent coating 306 be in being arranged on the recess of encapsulation and cover led chip, and luminous red colour system fluor and the YAG that carries out conversion that contains respectively led chip are fluor.As the concrete material that forms luminescent coating, can suitably use the light transmission inorganic materials of the silicon sol, glass etc. of the transparent resin that has excellent weather resistance of Resins, epoxy, urea-formaldehyde resin, silicone resin etc. or anti-opticity excellence.In addition, also can all contain diffusant with fluor.Can suitably use barium titanate, titanium oxide, aluminum oxide, silicon oxide, lime carbonate, silicon-dioxide etc. as concrete diffusant.
[model assembly 307]
Model assembly 307 can be protected led chip 302,304, electroconductibility electric wire 110 from outside atmosphere, contain the luminescent coating etc. of fluor and be provided with for the use that is adapted to photodiode.Generally speaking, model assembly 307 can use resin and form.In addition, can increase visual field degree of separating, but relax directive property, and more increase field-of-view angle from led chip by diffusant being contained at resin mould by containing fluor.And then the shape by model assembly 307 is made expectation, can have the luminous lens effect bringing and spread of shape from led chip.Therefore, model assembly 307 also can be a plurality of stacked structures.Particularly, convex lens shape, concavees lens shape, even luminous inspection surface observation and be elliptical shape, or the thing that this type of combination is a plurality of.As the concrete material of model assembly 307, mainly suitably use the light transmission inorganic materials etc. of the silicon sol, glass etc. of the transparent resin that has excellent weather resistance of Resins, epoxy, urea-formaldehyde resin, silicone resin etc. or anti-opticity excellence.In addition, can suitably use barium titanate, titanium oxide, aluminum oxide, silicon oxide, lime carbonate, silicon-dioxide etc. as diffusant.In addition, consider that specific refractory power also can use identical parts, for example silicone resin and form model assembly and luminescent coating.In the present application, diffusant or tinting material are contained at model assembly, be meant the painted hidden of fluor that luminous inspection surface side is observed.Also have, the fluor of painted finger the present application of fluor absorbs from the blue composition in the light of stronger outer light, and carries out luminous.Therefore, can observe and to be coloured to the xanchromatic state.Particularly according to the shape of model assemblies such as convex lens shape, enlarge painted and observe.Like this painted has preferred inadequately situation in the design.The diffusant that contains at model assembly is coloured to oyster white with model assembly, and tinting material is coloured to the look of expectation, can reach the state that loses painted vestige.Therefore, can't observe the color of fluor from so luminous inspection surface side.
In addition, the main light emission wavelength of the light that radiates from led chip is more than the 430nm, and when containing Photostabilised dose UV light absorber in model assembly, its weathering resistance aspect is preferred.
Embodiment
Below, enumerate embodiment and illustrate and relate to fluor of the present invention, light-emitting device, but be not limited to this embodiment.
Also have, in following embodiment, temperature profile is represented 25 ℃ luminosity is made 100% relative brightness.
In addition, particle diameter is according to the value of the air penetrant method of F, S.S.S.No. (FisheR is Sub Sieve SizeR system ' s No.).
In addition, twilight sunset after the rayed certain hour with 253.7nm, is made non-state of lighting a lamp with the electric light of excitation light source with room temperature (20 ℃).It is 0 that the benchmark of time is made the time rule of non-moment of lighting a lamp with the electric light of this excitation light source.With the brightness in the excitation light source irradiation during, measure the needed time till the brightness decay to 1/10 as 100% luminance reference.The result of this mensuration is determined persistence characteristic as benchmark.
Embodiment 1～80
The fluor of embodiment 1～80, the fluor of the embodiment relevant with embodiment 1.
The characteristic of the embodiment 1 to 80 of table 1 expression nitride phosphor of the present invention.
Table 1 (1)
Element Addition (ppm) Interpolation source molecular weight Reagent producer The element molecular weight Tone x Tone y Brightness Y (%) Quantum yield Q (%) Particle diameter (μ m) Twilight sunset (msec) 100 ℃ of temperature 200 ℃ of characteristics
1 Li 100 LiOH·H 2O 41.96 With the superfine 124-01212 of light reagent 6.94 0.585 0.407 205.5 211.8 2.5 28
2 Li 500 0.585 0.407 196.2 201.8 2.3 30 95.4 65.5
3 Na 100 Na 2CO 3 105.99 With the superfine 197-01585 of light reagent 22.99 0.584 0.407 210.9 215.9 2.6 14
4 Na 500 0.585 0.406 215.5 221.4 2.7 22 97.1 70.3
5 K 100 K 2CO 3 138.21 With the superfine 162-03495 of light reagent 39.1 0.585 0.406 209.8 216.4 2.5 24
6 K 500 0.585 0.407 210.2 216.4 2.6 26 96.1 66.1
7 Rb 100 RbCl 120.92 With the superfine 187-00321 of light reagent 8542 0.585 0.407 217.1 221.6 2.4 22
8 Rb 500 0.585 0.407 205.1 209.8 2.5 30 96.6 69.5
9 Cs 100 CsCl 168.36 With the superfine 035-01952 of light reagent 132.91 0.584 0.407 192.6 183.1 2.2 18
10 Cs 500 0.585 0.407 202.0 192.0 2.5 18 94.3 66.4
11 Mg 100 Mg(NO 3) 2 5.5％ With the superfine 134-00255 of light reagent 24.31 0.586 0.407 215.5 220.5 2.7 22
12 Mg 500 0.586 0.407 216.0 221.6 2.8 32 85.5 66.5
13 Sr 100 SrCl 2·H 2O 266.64 With the superfine 197-04185 of light reagent 87.62 0.586 0.406 212.4 202.3 2.4 22
14 Sr 500 0.584 0.407 206.7 195.9 2.5 26 97.3 70.8
15 Ba 100 BaCl 2·H 2O 244.26 With the superfine 029-00175 of light reagent 137.33 0.587 0.405 224.8 231.9 2.7 18
16 Ba 500 0.586 0.407 215.5 220.0 2.6 20 97.5 72.1
17 Ti 100 TiOSO 4·H 2O 177.98 Strange scholar field chemistry 020-78905 47.9 0.585 0.409 218.2 222.1 2.8 14
18 Ti 500 0.584 0.409 208.4 212.3 3.2 14 98.1 65.7
19 Zr 100 ZrO(NO 3) 2 267.3 Three Tianjin and chemistry 91.22 0.586 0.407 214.9 221.0 2.6 20
20 Zr 500 0.586 0.408 206.7 211.8 2.7 34 98.4 74.4
Table 1 (2)
Element Addition (ppm) Interpolation source molecular weight Reagent producer The element molecular weight Tone x Tone y Brightness Y (%) Quantum yield Q (%) Particle diameter (μ m) Twilight sunset (msec) 100 ℃ of temperature 200 ℃ of characteristics
21 Hf 100 HfCl 4 320.3 Three phyllody NO 51872 178.49 0.584 0.407 193.6 198.2 2.5 30
22 Hf 500 0.583 0.408 192.0 194.5 2.5 30 93.4 61.2
23 V 100 VCl 3 157.30 With the superfine 221-00452 of light reagent 50.94 0.585 0.407 214.9 220.5 3.1 26
24 V 500 0.582 0.411 164.7 166.5 3.1 26 97.9 69.9
25 Nb 100 Nb 2O 5 265.8 With the superfine 144-05332 of light reagent 92.91 0.584 0.408 190.7 193.8 2.3 26
26 Nb 500 0.583 0.409 191.1 192.7 2.5 26 99.1 74.8
27 Ta 100 TaCl 5 358.21 Strange scholar field chemistry 020-76055 180.95 0.585 0.408 218.2 222.8 2.6 18
28 Ta 500 0.583 0.411 190.9 192.0 2.7 18 96.5 64.6
29 Cr 100 Cr(NO 3) 3·9H 2O 400.14 With the superfine 033-03175 of light reagent 52 0.582 0.411 167.6 169.7 2.6 10
30 Cr 500 0.579 0.412 100.0 100.0 2.6 12 93.6 58.6
31 Mo 100 H 2MoO 4 179.98 The NAJARAI chemistry 95.94 0.583 0.402 197.3 200.2 2.5 20
32 Mo 500 0.581 0.410 174.3 175.4 2.6 32 97.9 72.7
33 W 100 H 2WO 4 249.88 With the superfine 209-03452 of light reagent 183.85 0.584 0.409 208.6 213.4 2.9 22
34 W 500 0.584 0.409 187.8 190.4 2.9 22 98.2 71.2
35 Re 100 RaCl 5 363.47 Three phyllody NO 58374 186.2 0.584 0.407 207.8 211.8 2.4 22
36 Re 500 0.583 0.409 193.6 196.1 2.5 22 93.7 65.6
37 Fe 100 FeCl 3·3H 2O 270.3 With the superfine 9-87 of light reagent 55.85 0.581 0.410 149.9 152.2 2.4 32
38 Fe 500 0.580 0.411 113.5 114.8 2.4 42 99.6 79.6
39 Co 100 Co(NO 3) 3·6H 2O 291.03 With the superfine 035-03755 of light reagent 58.93 0.585 0.409 177.4 180.9 2.6 16
40 Co 500 0.581 0.411 151.0 152.2 2.7 18 96.5 67.7
Table 1 (3)
Element Addition (ppm) Interpolation source molecular weight Reagent producer The element molecular weight Tone x Tone y Brightness Y (%) Quantum yield Q (%) Particle diameter (μ m) Twilight sunset (msec) 100 ℃ of temperature 200 ℃ of characteristics
41 Ir 100 IrCl 3 298.57 With the superfine 096-01601 of light reagent 192.22 0.583 0.410 195.7 200.3 2.6 22
42 Ir 500 0.581 0.410 183.7 186.5 2.4 22 97.5 70.1
43 Ni 100 NiCl 2·6H 2O 237.72 With the superfine 141-01062 of light reagent 58.71 0.582 0.410 163.0 165.6 2.7 12
44 Ni 500 0.580 0.411 112.0 113.4 2.8 20 98.3 72.5
45 Pd 100 PdCl 2 177.31 With the superfine 162-00053 of light reagent 106.42 0.583 0.409 191.0 193.6 2.5 20
46 Pd 500 0.582 0.410 166.5 168.4 2.4 22 98.6 73.0
47 Pt 100 HPtCl 6·6H 2O 517.90 With the superfine 169-02861 of light reagent 195.08 0.582 0.411 194.7 197.7 2.5 24
48 Pt 500 0.581 0.410 181.6 183.8 2.4 24 98.1 72.0
49 Ru 100 RuCl 3·9H 2O 244.2 Strange scholar field chemistry 020-68601 101.07 0.584 0.407 205.5 209.8 2.5 20
40 Ru 500 0.582 0.409 173.8 175.4 2.5 28 97.9 69.8
51 Cu 100 Cu(CH 3COO) 2·H 2O 199.65 With the superfine 3-402 of light reagent 63.54 0.586 0.406 214.9 193.6 2.5 24
52 Cu 500 0.586 0.406 208.2 168.3 2.6 32 97.8 70.6
53 Ag 100 Ag(NO 3) 3 169.8 With the superfine 198-00835 of light reagent 107.8 0.585 0.406 205.1 220.7 2.2 24
54 Ag 500 0.585 0.407 204.7 214.1 2.3 26 96.7 68.1
55 Au 100 HAuCl 4·4H 2O 411.9 With the superfine 077-00931 of light reagent 196.97 0.584 0.407 205.1 210.9 2.2 22
56 Au 500 0.583 0.409 204.7 209.8 2.4 24 98.2 71.2
57 Zn 100 Zn(NO 3) 2·6H 2O 297.49 With the superfine 265-01032 of light reagent 65.37 0.585 0.407 208.6 213.7 2.6 20
58 Zn 500 0.584 0.408 195.8 200.0 2.3 22 93.2 63.0
59 B 100 H 3BO 3 61.84 With the superfine 021-02195 of light reagent 10.81 0.588 0.405 234.6 244.6 3.1 20
60 B 500 0.588 0.405 237.9 248.1 3.3 22 96.9 69.9
Table 1 (4)
Element Addition (ppm) Interpolation source molecular weight Reagent producer The element molecular weight Tone x Tone y Brightness Y (%) Quantum yield Q (%) Particle diameter (μ m) Twilight sunset (msec) 100 ℃ of temperature 200 ℃ of characteristics
61 Al 100 Al(NO 3) 3·9H 2O 375.14 With the superfine 018-01945 of light reagent 26.98 0.585 0.407 181.2 186.3 2.5 22
62 Al 500 0.586 0.407 191.1 196.1 2.7 26 95.7 68.1
63 Ga 100 GaCl 2 176.09 Nichia Chemical Industries, Ltd's system 69.72 0.585 0.407 213.3 218.5 2.5 24
64 Ga 500 0.585 0.407 213.3 218.0 2.7 38 97.1 68.2
65 In 100 InCl 3 221.1 Nichia Chemical Industries, Ltd's system 114.82 0.585 0.407 210.2 215.3 2.5 26
66 In 500 0.585 0.407 204.7 208.9 2.4 22 96.9 64.6
67 Ge 100 GeO2 104.6 With the superfine 071-04552 of light reagent 72.59 0.585 0.407 199.8 204.6 2.4 24
68 Ge 500 0.584 0.408 186.9 190.7 2.5 24 96.1 63.8
69 Sn 100 Sn(CH 3COO) 2 236.78(90％) Strange scholar field chemistry Iot F07563D+E8 118.69 0.585 0.407 201.3 205.7 2.2 22
60 Sn 500 0.584 0.408 185.4 188.4 2.2 24 97.8 66.1
71 Pb 100 Pb(NO 3) 2 331.21 With the superfine 124-00612 of light reagent 207.20 0.585 0.407 203.1 192.9 2.5 20
72 Pb 500 0.585 0.407 208.2 198.2 2.4 26 97.0 70.4
73 P 100 (NH 4) 2PO 4 132.08 With the superfine 016-03325 of light reagent 30.97 0.584 0.407 204.7 209.3 2.2 28
74 P 500 0.584 0.408 202.4 205.7 2.3 22 95.4 60.8
75 Sb 100 Sb 2O 3 291.5 With the superfine 016-11652 of light reagent 121.75 0.585 0.407 207.1 211.4 2.5 22
76 Sb 500 0.584 0.408 186.3 189.5 2.1 24 96.7 61.0
77 Bi 100 Bi(NO 3) 3·5H 2O 485.07 With the superfine 024-09042 of light reagent 208.98 0.584 0.407 205.5 210.3 2.2 24
78 Bi 500 0.583 0.408 173.4 176.8 2.1 26 96.7 65.1
79 S 100 (NH 4) 2SO 4 132 With the superfine 019-03435 of light reagent 32.06 0.585 0.407 197.8 203.4 2.5 26
80 S 500 0.586 0.407 200.4 209.3 2.5 34 97.3 69.8
The figure of the luminescent spectrum when in addition, Fig. 5 represents to excite with Ex=460nm the nitride phosphor of embodiment 60.Fig. 6 represents to implement the figure of excitation spectrum of the nitride phosphor of shape 60.Fig. 7 represents to implement the figure of reflection spectrum of the nitride phosphor of shape 60.
Fluor of the present invention is with general formula L XM YN ((2/3) X+ (4/3) Y): R system or L XM YO ZN ((2/3) X+ (4/3) Y-(2/3) Z): the nitride phosphor that R is represented, and above-mentioned nitride phosphor to contain with above-mentioned L, above-mentioned M, above-mentioned O, above-mentioned N, above-mentioned R be different element (below, abbreviate " different element " as).In this general formula, embodiment 1 to 80 is with Ca 0.985Eu 0.015Si 5N 7.990O 0.00225Represented nitride phosphor, and to contain with above-mentioned L, above-mentioned M, above-mentioned O, above-mentioned N, above-mentioned R be different elements.Table 1 is the result of characteristic who checks the nitride phosphor of embodiment 1 to 80.The raw material ratio of mixture of table 1, the person that represents the raw material with mol ratio.In embodiment 1 to 80, Eu concentration 0.015.Eu concentration is to the mol ratio of the volumetric molar concentration of Ca.In addition, to the fluor after synthetic vary in weight the addition 100ppm or the 500ppm concentration of element.By adding this difference element, promptly can carry out the adjustment of brightness, the adjustment of quantum yield.In addition, because of crucible, when the stove material causes Elements Diffusion, and the effect in order to confirm to produce because of the element that contains at raw material, then add different elements are confirmed this difference element at raw material effect.Therefore, in the use of reality, as because of crucible, when the stove material causes elemental diffusion, more consider demulcent condition (add the different elements of consciousness when raw material still less).
In the present embodiment, at first the Ca with raw material is ground into 1～15 μ m, and carries out nitrogenize in nitrogen atmosphere.After this, the nitride with Ca is ground into 0.1～10 μ m.The Ca of the raw material of weighing 20g and carry out nitrogenize.
Si with raw material is ground into 1～15 μ m in the same manner, and carries out nitrogenize in nitrogen atmosphere.After this, the nitride with Si is ground into 0.1～10 μ m.The Si of the raw material of weighing 20g and carry out nitrogenize.
Then, will contain the compd E u of the chemical combination wet mixing of different elements at Eu 2O 3As the compound that different element contained, with H 3BO 3When illustrating for example, at first, the compd E u of the Eu of weighing 20g 2O 3, 3.65g H 3BO 3With H 3BO 3During as solution, with H 3BO 3As solution mixing Eu 2O 3In solution, and carry out drying.After drying, in oxidizing atmosphere, burnt till about 5 hours with 700 ℃～800 ℃.Make the europium sesquioxide that is added with B therefrom.After this burns till, the mixture of Eu and B is ground into 0.1～10 μ m.
In the nitrogen atmosphere, the mixture of nitride, Eu and the B of the nitride of Ca, Si is mixed.In embodiment 1 to 80, contain mixture ratio (mol ratio) Ca: Si: Eu=1.985: 5: 0.015 at each element of raw material.Under the state that can form this mixture ratio, the Ca of weighing 5.73g 3N 2(molecular weight 148.26), the Si of 13.9g 3N 4(molecular weight 140.31), the Eu of 0.37g and the mixture of B (wherein, Eu is 0.31), and mix.The amount of the B that is added becomes 500ppm therefrom.
During the situation of embodiment 1 to 80, replace above-mentioned boron (B) and, make it to become under the state of 100ppm, 500ppm with the different elements shown in the table 1, carry out Eu and different elements mixing, burn till, pulverize after, carry out weighing again.Be added on the different elements of the nitride phosphor of embodiment 1 to 80, LiOH.H is arranged 2O (with the superfine 124-01212 of light reagent), Na 2CO 3(with the superfine 197-01585 of light reagent), K 2CO 3(with the superfine 162-03495 of light reagent), R are bCl (with the superfine 187-00321 of light reagent) CsCl (with the superfine 035-01952 of light reagent), Mg (NO 3) 2(with the superfine 134-00255 of light reagent) CaCl.6H 2O (with the light reagent) SrCl 2.6H 2O (with the superfine 197-04185 of light reagent), BaCl 2.2H 2O (with the superfine 029-00175 of light reagent), TiOSO 4.H 2O (strange scholar field chemistry 020-78905), ZRO (NO 3) 2(three Tianjin and chemistry), HfCl 4(three phyllody No.51872), VCl 3(with the superfine 221-00452 of light reagent), Nb 2O 5(with the superfine 144-05332 of light reagent), TaCl 5(strange scholar field chemistry 020-76055), Cr (NO 3) 3.9H 2O (with the superfine 033-03175 of light reagent), H 2WO 4(with the superfine 209-03452 of light reagent), ReCl 5(three phyllody No.58374), FeCl 3.3H 2O (with the superfine 9-87 of light reagent), R are uCl 3.2H 2O (strange scholar field chemistry 020-68601), Co (NO 3) 3.6H 2O (with the superfine 035-03755 of light reagent), NiCl 2.H 2O (with the superfine 141-01062 of light reagent), IRCl 3(with the superfine 096-01601 of light reagent), PdCl 2(with the superfine 162-00053 of light reagent), H 2PtCl 6.6H 2O (with the superfine 169-02861 of light reagent), Cu (CH 3COO) 2.H 2O (with the superfine 3-402 of light reagent), AgNO 3(with the superfine 198-00835 of light reagent), HAuCl 4.4H 2O (with the superfine 077-00931 of light reagent), Zn (NO 3) 2.6H 2O (with the superfine 265-01032 of light reagent), H 3BO 3(with the superfine 021-02195 of light reagent), Al (NO 3) 3.9H 2O (with the superfine 018-01945 of light reagent), GaCl 3(Nichia Chemical Industries, Ltd's system), InCl 3(Nichia Chemical Industries, Ltd's system), GeO 2(with the superfine 071-04552 of light reagent), Sn (CH 3COO) 2(strange scholar field chemistry lotF07563D), Pb (NO 3) 2(with the superfine 124-00612 of light reagent), (NH 4) 2HPO 4(with the superfine 016-03325 of light reagent), Sb 2O 3(with the superfine 0164-11652 of light reagent), Bi (NO 3) 3.5H 2O (with the superfine 019-03435 of light reagent), (NH 4) 2SO 4(with the superfine 019-03435 of light reagent).
The concentration of the different elements in this compounds is to the Ca that is added 2Si 5N 8: Eu is weighing and interpolation with the state that can become 100ppm or 500ppm.
To have the compound of above-mentioned different elements and burn till.Firing condition is in ammonia atmosphere, is directed into boron nitride crucible, is heated up lentamente about 5 hours by room temperature, and carries out 5 hours burn till with about 1350 ℃, makes it be cooled to room temperature through 5 hours lentamente.Make different elements disperse because of burning till, the situation that does not contain different elements in final product is also arranged.Even contain different elements, also addition was still less and remaining 0.1ppm～hundreds of ppm degree more originally.
The brightness and the quantum yield of the nitride phosphor of embodiment 1 to 80, expression during with the Cr that adds 500ppm (quantum yield of embodiment 30) make 100%, as the relative value of benchmark.
The purpose of burning till not only can be carried out solid state reaction simply, and it is fabulous and can grow to suitable particle diameter also can to obtain crystallinity.The material that will be added on raw material in order to the growth of help crystallisation is called and melts agent (fusing assistant).In addition, fusing assistant not only can promote particle to grow up, and it is passable to the merit of parent grid also to have an activator of importing.I family element is for example represented with lower temperature to exist in the element of the state of dissolving fluor grain circle when burning till, and form the solution of dissolving fluor composition, and promote the particle of fluor.Fluor forms the shape that is easy to absorb excitation energy therefrom.
What contain embodiment 1 to 10 is the fluor of the I family element formed of b, Cs by Li, Na, K, R, has high brightness and high-quantum efficiency.This is to consider that I family element can promote the particle growth and import the fusing assistant effect of activator to the parent grid.Embodiment 1 to 10 can regulate its brightness according to the addition of adjusting I family element.
Embodiment 11 to 16,57 and 58 is quite at the II family element of above-mentioned L, contains Mg, Sr, Ba, Zn are 100ppm or 500ppm.Nitride phosphor can carry out the adjustment of brightness according to the amount of adjusting L.
Contain the V group element that P, Sb, Bi formed by I family element that Sn, Pb formed, embodiment 73 to 78, embodiment 79 of the iii group element that B, Al, Ga, In formed by IV family element that Ti, ZR, Hf formed, embodiment 51 to 56, the embodiment 69 to 72 of embodiment 17 to 22 and 80 nitride phosphor, can make high brightness by the VI family element that S formed by I family element that Cu, Ag, Au formed, embodiment 59 to 66.
Contain embodiment 23 to 28 by V group element that V, Nb, Ta formed, embodiment 29 to 34 by VI family element that Cr, Mo, W formed, embodiment 35 and 36 by VII family element that Re formed, embodiment 37 to 50 be the nitride phosphor of the group VIII element formed of u by Fe, Co, IR system, Ni, Pd, Pt, R, according to adjusting the adjustment that its amount can carry out brightness.
In the present embodiment, consider in the firing process that crucible is by etch, and the element of formation crucible is sneaked into to nitride phosphor from crucible.Herein, the nitride phosphor of embodiment, owing to use the crucible of boron nitride material, and in ammonia atmosphere, burn till, so consider crucible by etch, and boron is sneaked into to nitride phosphor.During this situation, shown in embodiment 59 and 60, nitride phosphor can improve brightness and quantum yield by containing boron.
Therefore, be target with the effect that improves brightness and quantum yield, can use the crucible of boron nitride material energetically.
On the other hand, when using the crucible of molybdenum materials matter, sneak into to nitride phosphor, and during this situation, shown in embodiment 32, molybdenum reduces brightness and quantum yield though consider molybdenum.Therefore, be compared to molybdenum crucible, it is preferred then using boron nitride crucible.So, can from embodiment 1 to 80 can predict to a certain degree because of of the influence of contained element such as crucible, stove material to nitride phosphor.
Even from embodiment 1 to 80 different elements when containing hundreds of ppm concentration, can not have the situation about significantly reducing that produces luminosity, luminous efficiency yet, and carry out distinct orange～red luminous luminescent material by the excitation light source of 450nm～470nm to provide.
In addition, in table 1, temperature profile represent the pyritous of nitride phosphor luminous good not, even pyritous attenuation smaller is provided with the near surface of this nitride phosphor at luminous element, can carry out stable luminous.When being 95～100%, 200 ℃ when being 97～100%, 100 ℃ during 1 to 80,35 ℃ of this embodiment is 58～80%.The temperature profile of the nitride phosphor of hence one can see that this embodiment 1 to 80 is fabulous.
According to above embodiment 1～80, particularly during the B of～hundreds of ppms tens of to add, when adding the Cr of 500ppm is benchmark, and become that brightness is 234.6%, quantum yield is 244.6% (adding the B of 100ppm), brightness is 237.9%, quantum yield is 248.1% (adding the B of 500ppm), and also obviously improves luminous efficiency.In addition,, also can use Ba, Sr, Ca-Sr with replacement Ca though be not documented in embodiment, and also can be to obtain identical effect.
The nitride phosphor of embodiment 1 to 80 when the excitation light source according to 460nm is excited, has peak wavelength near 690nm.
The twilight sunset 14msec of embodiment 3, the twilight sunset 18msec of embodiment 9, the twilight sunset of embodiment 11 is 22msec, the twilight sunset 18msec of embodiment 15, and the twilight sunset of embodiment 17 is 14mesc, the twilight sunset 18mesc of embodiment 27, the twilight sunset of embodiment 29 is 10msec, and the twilight sunset of embodiment 39 is 16msec, and the twilight sunset of embodiment 43 is 12msec, the twilight sunset of embodiment 59 is 20msec, and the twilight sunset of embodiment 61 is 22msec etc.So, Na, Ti, Mg, Al, B, Cr, Ni etc. have the effect that can shorten twilight sunset.
When the composition of the nitride phosphor of analysis embodiment 1 to 80 was formed, the Li of the addition of 500ppm, Na, K, R were b, Cs, Mg, W, Cu, Ag, Au, Zn, Ga, In, Ge, Sn, Pb, P, Sb, Bi etc., the amount that only residual 100ppm is following.The also only residual addition more originally of other different elements amount still less.For example, add the only residual 400ppm of B of 500ppm.This is to be regarded as in firing process, the cause that different elements disperse.
Embodiment 81
The light-emitting device of embodiment 81 uses the fluor of embodiment 15 and the white color system light-emitting device of the additional red composition that constitutes.Also have, the light-emitting device of present embodiment 81 is light-emitting devices of Class1 shown in Figure 1.In addition, Fig. 8 is the figure of tristimulus coordinates of the light-emitting device of expression present embodiment 81.
The luminous element 10 of embodiment 81 has stacked gradually n on sapphire substrate 1 +GaN:Si, n-AlGaN:Si, n-GaN, GaInNQWs, P-GaN:Mg, P-AlGaN:Mg, P-GaN:Mg and as semiconductor layer 2.Then, this n +The part of GaN:Si layer is exposed according to etching mode and is formed with n type electrode.In addition, on the P-GaN:Mg layer, be formed with p type electrode.Lead frame 13 uses ferruginous copper.Luminous element 10 is bonded on the substantial middle portion of the cup bottom surface that lead-in wire 13a is installed.Conducting wire 14 uses gold, imposes Ni in order to the projection 4 of conduction connection electrode 3 and conducting wire 14 and electroplates.Fluor 11 is that fluor mixes and uses with the fluor of embodiment 15 and YAG.Coating member 12 uses with institute's certainty ratio Resins, epoxy and diffusant, barium titanate, titanium oxide and above-mentioned fluor 11 mixers.Model assembly 15 uses Resins, epoxy.The light-emitting device of the bullet cut of embodiment 81, the top that is the radius 2～4mm of modular unit 15, highly about 7～10mm is the round tube type of hemisphere.
When circulating current during to the light-emitting device 1 of this embodiment 81, then the peak wavelength blue based light-emitting device 10 that is roughly 460nm and has the 1st luminescent spectrum that can excited fluophor 11 carries out luminously, and the fluor 11 that covers semiconductor layer 2 will have the part of the light of the 1st luminescent spectrum and carry out tone reversal.Particularly, the fluor of embodiment 15 light that will have 2nd luminescent spectrum different with the 1st luminescent spectrum carries out luminous.In addition, the YAG that contains in fluor 11 is a fluor, be excited via the light with the 1st luminescent spectrum, and the light that will have the 3rd luminescent spectrum carries out luminous.The white color system light-emitting device of embodiment 81 will have the light intermingling of the 1st, the 2nd and the 3rd luminescent spectrum and the reddish light that forms colour mixture carries out luminous.
Use the fluor of mix embodiment 15 and the yttrium that is activated with cerium. gadolinium. aluminum oxide be fluor (Y-Gd-Al-O:Ce) fluor and as the fluor 11 of the light-emitting device of embodiment 81.Embodiment 15 is the Ca that add B 2Si 5N 8: the nitride phosphor of Eu.On the other hand, make the fluor do not contain embodiment 15 as a comparison, only use the yttrium that is activated with cerium. gadolinium. aluminum oxide is a fluor and as the light-emitting device of the Class1 of fluor 11.The light-emitting device of embodiment 81 is the light-emitting device of usefulness relatively, is to use (Y 0.8Gd 0.2) 3Al 5O 12: the fluor of Ce and as yttrium. gadolinium. aluminum oxide is a fluor.Relatively the light-emitting device of usefulness carries out luminous with the combination of the fluor of blue based light-emitting device and (Y-Gd)-Al-O:Ce.The yttrium that use is activated with cerium. gallium. aluminum oxide is fluor Y 3(Al 0.8Gd 0.2) 5O 12: Ce replaces the yttrium that is activated with cerium. gadolinium. and aluminum oxide is that fluor then serves as preferred.
In the light-emitting device of embodiment 81, the weight ratio of fluor 11 is made coating member: the fluor of fluor (Y-Gd-Al-O:Ce): embodiment 15: 10: 3.8: 0.6.On the other hand, the fluor of comparative example is the weight ratio of the fluor=10: 3.6 with coating member (Y-Gd-Al-O:Ce) and mixing.
The light-emitting device of embodiment 81 and the light-emitting device of the comparative example of the fluor that uses blue based light-emitting device and Y-Gd-Al-O:Ce are compared.Table 2 is measurement results of the light-emitting device of the expression light-emitting device of embodiment 81 and comparative example.Fluor with Y-Gd-Al-O:Ce in the table 2 slightly is designated as YAG.
Table 2
Electric current I F (mA) Voltage VF (V) Radiometric analysis RadiometR is ic (mW) Photometry PhotometR is ic (lm) Peak wavelength Peak (nm) Half value wide cut FWHM (nm)
Blue led 20 4.05 14.78 0.955 464.02 19.35
Comparative example blue led+YAG 20 3.75 9.59 3.042 463.47 150.73
Embodiment 81 blue leds+YAG+ nitride phosphor 20 3.80 5.84 1.890 596.00 196.36
Apparent wavelength Dominant (nm) Tone x Tone y Colour temperature Tcp (K) Average color developing Pa Luminous efficiency (lm/W)
Blue led 468.05 0.134 0.057 - - 11.8
Comparative example blue led+YAG 568.85 0.348 0.367 4939 78 40.6
Embodiment 81 blue leds+YAG+ nitride phosphor 582.75 0.454 0.416 2828 76 24.9
The light-emitting device of embodiment 81 more improves its color developing than the light-emitting device of comparative example.It is inadequate that number R9 is estimated in the special colour developing of the light-emitting device of comparative example, and the light-emitting device of embodiment 81 carries out the improvement of R9.It is the value of measuring the chroma offset that departs from from the higher red reference colour of chroma that number R9 is estimated in special colour developing.In addition, other special colour developing is estimated number R8, R10 etc. and is also improved the value that becomes more near 100%.Lamp efficient shows high numerical value.
All carry out blended fluor 11 with coating member 12, use though mix the fluor of Y-Gd-Al-O:Ce and nitride phosphor, because these 2 density of phosphor be different, so generally speaking, density is higher, particle diameter is healed little person, then more sedimentation morning.Therefore, the sedimentation of going ahead of the rest of the fluor of Y-Gd-Al-O:Ce, and nitride phosphor sedimentation then.So,, and on the tone of light-emitting device, also produce the phenomenon of mottle even use identical coating member 12 and fluor 11.Therefore, with the particle diameter of nitride phosphor be controlled to fixed size, and make the fluor of Y-Gd-Al-O:Ce and nitride phosphor roughly sedimentation simultaneously and can be improved as and not produce mottle then for preferred.
Embodiment 82.
The light-emitting device of embodiments of the invention 82 is light-emitting devices of form 2 (surface installing type) shown in Figure 2.The light-emitting device of this embodiment 82 uses the luminous luminous element that can carry out blue light (have peak wavelength and be the InGaN semiconductor layer of the 460nm of the blue region luminous element as luminescent layer) as luminous element 101.But the present invention is not limited to carry out the luminous luminous element of blue light, and also can use the luminous luminous element that for example can carry out the UV-light of 380～400nm.
More specifically, luminous element 101 is formed with the first n type semiconductor layer of p type semiconductor layer (figure), and this p type semiconductor layer and n type semiconductor layer intermediary's resistance electrode and be connected the conducting wire 104 that it is linked to lead-in wire electrode 102 respectively.In addition, be formed with insulated enclosure material 103, and prevent short circuit phenomenon with the state of the periphery that can cover lead-in wire electrode 102.The window portion 107 of light transmission is set above luminous element 101, and it is from the top cover 106 on the top of encapsulation 105 and extend.Inner face in the window portion 107 of this light transmission roughly is coated with the uniform mixture of fluor 108 of the present invention and coating member 109 all sidedly.Herein, the light-emitting device of embodiment 82 uses the fluor, (Ca of embodiment 60 0.93 'Eu 0.05 'Mn 0.02) 10(PO 4) 6Br 2Fluor, Y 3(Al 0.8Ga 0.2) 5O 12: the fluor of Ce.One side that encapsulation 105 is got its bight is the square of 8mm～12mm.
With luminous element 101 luminous blueness system in the light of the indirect that reflects with reflector and rayed that self-emission device 101 directly penetrates at fluor 108, and can carry out the luminous of white color system.
The light-emitting device that uses processing as above and form and when making the White LED electric light, its yield rate can reach 99%.So, according to the photodiode of present embodiment 81, promptly can provide productivity good and reliability is higher and light-emitting device that the jug-handled phenomenon of tone is less.
Embodiment 83.
The light-emitting device of embodiment 83 is the light-emitting device of form 3 shown in Figure 8 (type at interval).
In the light-emitting device of present embodiment 83, use the fluor that uses embodiment 15 at the fluor of wall 16.Also use the fluor of embodiment 15 in the cup of installation lead-in wire 13a.But because the use fluor is at wall 16, so need only coating member 12 in the cup of installation lead-in wire 13a.
The light-emitting device that is so constituted, the part of the light of self-emission device 10 and radiation are for by wall 16 time, and the fluor by embodiment 15 imposes wavelength conversion.The light that so imposes the light of wavelength conversion and carry out the blueness of wavelength conversion via fluor mixes, its result, and the light of white color system is from the surface of wall 16 and radiate externally.
Below, the embodiment 84～109 that relates to embodiments of the present invention 2 is described.
Embodiment 84 to 87.
Table 3 is characteristics of the nitride phosphor of expression embodiment 84 to 87.
In addition, Fig. 9 is the figure of the luminescent spectrum of expression when exciting the nitride phosphor of embodiment 86 with the Ex=460nm utmost point.Figure 10 is the figure of excitation spectrum of the nitride phosphor of expression embodiment 86.Figure 11 is the figure of reflection spectrum of the nitride phosphor of expression embodiment 86.Figure 12 is a SEM photo of taking the nitride phosphor of embodiment 86.Figure 12 A takes with 1000 times.Figure 12 B takes with 5000 times.
Table 3
Embodiment The addition of B (ppm) Tone x Tone y Luminosity (%) Quantum yield (%)
84 10 0.596 0.398 100 100
85 200 0.598 0.397 107 108
86 500 0.598 0.396 112 113
87 1000 0.598 0.396 110 112
Embodiment 84 to 87 is with (Ca 0.97Eu 0.03) 2Si 5N 8Represented nitride phosphor, and contain quantitative to some extent B.Nitride phosphor with embodiment 84 is a benchmark, and represents luminosity, quantum yield with relative value.
In embodiment 84 to 87, Eu concentration 0.03.Eu concentration is with respect to the mol ratio of the volumetric molar concentration of Ca.
At first, the Ca of raw material is ground into 1～15 μ m, and in nitrogen atmosphere, carries out nitrogenize.After this, the nitride with Ca is ground into 0.1～10 μ m.The Ca of the raw material of weighing 20g also carries out nitrogenize.
Si with raw material is ground into 1～15 μ m in the same manner, and carries out nitrogenize in nitrogen atmosphere.After this, the nitride with Si is ground into 0.1～10 μ m.The Si of the raw material of weighing 20g also carries out nitrogenize.
Then, with the compound H of B 3BO 3Wet mixing is at the compd E u of Eu 2O 3In.The compd E u of the Eu of weighing 20g 2O 3, and quantitative H 3BO 3With H 3BO 3Behind solution, be blended in Eu 2O 3In and carry out drying.After drying, in oxidizing atmosphere, burnt till about 5 hours with 700 ℃～800 ℃.Make the europium sesquioxide that is added with B therefrom.After this burns till, the mixture of Eu and B is ground into 0.1～10 μ m.
The mixture of nitride, Eu and the B of the nitride of Ca, Si is mixed in nitrogen atmosphere.In embodiment 84 to 87, the CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Mixture ratio (mol ratio), be to can be adjusted to Ca: Si: Eu=1.94: 5: 0.06.Shown in this mixture ratio, with Ca 3N 2(molecular weight 148.26), Si 3N 4The mixture of (molecular weight 140.31) its Eu of weighing and B, and mix.The addition of B is to the molecular weight of last composition and be 10ppm, 200ppm, 500ppm, 1000ppm.
The mixing above-claimed cpd also burns till.Firing condition is in ammonia atmosphere, and above-claimed cpd is fed into crucible, from room temperature and Rushing-water heats up slowly, approximately burns till 5 hours with about 1600 ℃, and is cooled to room temperature lentamente.Generally speaking,, also remain in the composition, but the part of B is dispersed by burning till even the B that is added burns till, and in final product, only remaining addition less amount more originally.
The luminosity and the quantum yield of the nitride phosphor of embodiment 84 to 87 are that embodiment 84 is made 100%, and as benchmark and represented with relative value.
When demonstrating the B that adds below the 10000ppm by table 3, particularly add the above 1000ppm of 1ppm when following, the value that its luminosity, quantum yield are all higher.
The median size of the nitride phosphor of embodiment 84 to 87 is 6.3 to 7.8 μ m.In addition, the fluor in embodiment 84 to 87 contains the oxygen of 0.5～1.2 weight %.
The nitride phosphor of embodiment 84 to 87 is to use the crucible of boron nitride material, and burns till in ammonia atmosphere.
The nitride phosphor of embodiment 84 to 87, its temperature profile are fabulous.The temperature profile of the nitride phosphor of embodiment 86 then is 70% when being 97%, 200 ℃ in the time of 100 ℃.
The nitride phosphor of embodiment 84 to 87 when the excitation light source by 460nm is excited, has peak wavelength near 609nm.
(embodiment 88 to 92)
The characteristic of the nitride phosphor of table 4 expression embodiment 88 to 92.
Table 4
Embodiment The addition of B Tone Tone Luminosity Quantum yield
(ppm) x y (％) (％)
88 10 0.596 0.396 100 100
89 200 0.598 0.396 100 100
90 500 0.598 0.396 100 100
91 1000 0.598 0.396 105 104
92 10000 0.598 0.396 102 101
Embodiment 88 to 92 is with (Ca 0.97Eu 0.03) 2Si 5N 8Represented nitride phosphor, and contain quantitative to some extent B.Nitride phosphor with embodiment 88 is a benchmark, and represents luminosity, quantum yield with relative value.
In embodiment 88 to 92, Eu concentration 0.03.Eu concentration is the mol ratio with respect to the volumetric molar concentration of Ca.
The manufacture method of embodiment 88 to 92 and embodiment 84 to 87 is different.
At first, the Ca of raw material is ground into 1～15 μ m, and in nitrogen atmosphere, carries out nitrogenize.After this, the nitride with Ca is ground into 0.1～10 μ m.The Ca of the raw material of weighing 20g also carries out nitrogenize.
Similarly the Si with raw material is ground into 1～15 μ m, and carries out nitrogenize in nitrogen atmosphere.After this, the nitride with Si is ground into 0.1～10 μ m.The Si of the raw material of weighing 20g also carries out nitrogenize.
With dry type with the nitride of Ca, the nitride of Si, the compd E u of Eu 2O 3, B mixture H 3BO 3Mix.Use the compd E u of the Eu of weighing 20g 2O 3, the quantitative H of weighing 3BO 3In embodiment 88 to 92, the CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Mixture ratio (mol ratio), can be adjusted into Ca: Si: Eu=1.94: 5: 0.06.The addition of B is to the molecular weight of last composition and be 10ppm, 200ppm, 500ppm, 1000ppm, 10000ppm.
The mixing above-claimed cpd also burns till.Firing condition is in ammonia atmosphere, and above-claimed cpd is fed into crucible, from room temperature and Rushing-water heats up slowly, with about 1600 ℃ and burnt till about 5 hours, and is cooled to room temperature lentamente.
The luminosity and the quantum yield of the nitride phosphor of embodiment 88 to 92 make 100% with embodiment 88, and as benchmark and represented with relative value.
When demonstrating the B that adds below the 10000ppm by table 4, its luminosity, quantum yield all show higher value.
Median size 6.0 to the 7.2 μ m of the nitride phosphor of embodiment 88 to 92.Oxygen concn 0.7～1.0 weight %.
(embodiment 93 to 98)
Table 5 is characteristics of the nitride phosphor of expression embodiment 93 to 98.
Table 5
Embodiment The addition of B (ppm) Tone x Tone y Luminosity (%) Quantum yield (%)
93 10 0.618 0.375 100 100
94 100 0.619 0.374 104 107
95 200 0.620 0.373 105 109
96 500 0.618 0.376 107 105
97 1000 0.620 0.373 97 102
98 5000 0.625 0.368 95 110
Embodiment 93 to 98 is with (Sr 0.97Eu 0.03) 2Si 5N 8Represented nitride phosphor, and contain quantitative to some extent B.Nitride phosphor with embodiment 93 is a benchmark, and represents luminosity, quantum yield with relative value.
In embodiment 93 to 98, Eu concentration is 0.03.Eu concentration is the mol ratio with respect to the Sr volumetric molar concentration.
In embodiment 93 to 98, according to making with embodiment 84 to 87 roughly the same manufacture method.Embodiment 93 to 98 uses Sr to replace embodiment 84 to 87 employed Ca.Embodiment 84 to 87 is with about 1600 ℃ and burn till, and embodiment 93 to 98 approximately burns till with 1350 ℃.
When being added the B below the 10000ppm by table 5, particularly add the above 5000ppm of 10ppm when following, luminosity, quantum yield all show higher value.
Median size 2.1 to the 4.7 μ m of the nitride phosphor of embodiment 93 to 98.Oxygen concn is 0.3～1.1 weight %.
(embodiment 99 to 103)
The characteristic of the nitride phosphor of table 6 expression embodiment 99 to 103.
Table 6
Embodiment The addition of B (ppm) Tone x Tone y Luminosity (%) Quantum yield (%)
99 10 0.629 0.364 100 100
100 100 0.628 0.365 101 101
101 500 0.629 0.364 102 103
102 1000 0.628 0.365 98 98
103 5000 0.629 0.364 92 97
Embodiment 99 to 103 is with (Sr 0.97Eu 0.03) 2Si 5N 8Represented nitride phosphor, and contain quantitative to some extent B.With the nitride phosphor of embodiment 93 is benchmark, and shows luminosity, quantum yield with relative value.
In embodiment 99 to 103, Eu concentration is 0.03.Eu concentration is the mol ratio with respect to the volumetric molar concentration of Sr.
In embodiment 99 to 103, according to making with embodiment 84 to 87 roughly the same manufacture method.Embodiment 99 to 103 uses Sr to replace embodiment 84 to 87 employed Ca.
When being added the B below the 1000ppm by table 6, particularly add the above 500ppm of 10ppm when following, luminosity, quantum yield are all represented higher value.
The median size of the nitride phosphor of embodiment 99 to 103 is 3.2 to 3.9 μ m.
(embodiment 104 to 109)
The characteristic of the nitride phosphor of table 7 expression embodiment 104 to 109.
Table 7
Embodiment The addition of B (ppm) Tone x Tone y Luminosity (%) Quantum yield (%)
104 10 0.636 0.357 100 100
105 100 0.635 0.357 100 100
106 200 0.636 0.356 102 103
107 500 0.636 0.356 101 102
108 1000 0.636 0.356 98 99
109 5000 0.636 0.356 88 105
Embodiment 104 to 109 is with (Ca 0.285Sr 0.685Eu 0.03) 2Si 5N 8Represented nitride phosphor, and contain quantitative to some extent B.With the nitride phosphor of embodiment 104 is benchmark, and represents luminosity, quantum yield with relative value.
In embodiment 104 to 109, Eu concentration is 0.03.Eu concentration is the mol ratio with respect to the volumetric molar concentration of the mixture of Ca and Sr.
In embodiment 104 to 109, according to making with embodiment 84 to 87 roughly the same manufacture method.Embodiment 104 to 109 uses the mixture of Ca and Sr, and to replace embodiment 84 to 87 employed Ca, the mol ratio of Ca and Sr is 3.7.
When applying B below the 5000ppm by table 7, particularly add the above 1000ppm of 10ppm when following, luminosity, quantum yield all show higher value.
The median size of the nitride phosphor of embodiment 104 to 109 is 1.6 to 2.0.
＜relate to the embodiment 110～169 of embodiment 3 〉
Embodiment 110 to 124.
Embodiment 110 to 124 makes substrate nitride phosphor Ca-Si-N:Eu, the fluor that the activator WR of WR system carries out various changes.Table 8 expression is substrate nitride phosphor Ca-Si-N:Eu, and the activator WR of WR system carries out the chemical property and the physical property of fluor of the embodiment 110 to 124 of various changes.Figure 14 be expression with substrate nitride phosphor Ca-Si-N:Eu, the activator WR of WR system system system carries out the luminosity graphic representation relatively of fluor of the embodiment 110 to 124 of various changes.
Table 8
Eu concentration Uncommon great soil group element Add concentration Ionic radius (_) Tone x Tone y Luminosity (%) Quantum yield (%) Peak wavelength (nm) Twilight sunset 1/10 (ms) Amount
O (％) N (％)
Comparative example 1 0.0075 - - 1.13 0.581 0.410 100 100 609 18.5 1.3 30.0
Embodiment 110 0.0075 Sc 0.015 0.83 0.579 0.412 78.4 77.6 609 11.0 1.4 27.9
Embodiment 111 0.0075 Y 0.015 1.06 0.582 0.409 98.2 99.1 609 6.5 1.2 30.8
Embodiment 112 0.0075 La 0.015 1.22 0.583 0.409 111.4 111.9 609 12.5 1.1 33.5
Embodiment 113 0.0075 Ce 0.015 1.18 0.582 0.409 92.8 94.7 609 20.5 1.3 31.1
Embodiment 114 0.0075 Pr 0.015 1.16 0.586 0.408 105.4 106.8 609 23.5 1.4 30.4
Embodiment 115 0.0075 Nd 0.015 1.15 0.582 0.409 87.4 91.2 621 74.5 1.3 31.8
Embodiment 116 0.0075 Sm 0.015 1.13 0.582 0.410 51.1 50.8 608 2.5 1.3 31.5
Embodiment 117 0.0075 Gd 0.015 1.11 0.582 0.409 96.4 97.2 609 44.5 1.4 30.2
Embodiment 118 0.0075 Tb 0.015 1.09 0.582 0.409 99.1 100.4 610 26.0 1.3 30.7
Embodiment 119 0.0075 Dy 0.015 1.07 0.585 0.409 96.4 96.7 609 41.5 1.5 30.3
Embodiment 120 0.0075 Ho 0.015 1.05 0.584 0.410 89.7 89.5 609 11.0 1.4 30.0
Embodiment 121 0.0075 Er 0.015 1.04 0.583 0.410 89.4 89.1 609 8.5 1.3 29.9
Embodiment 122 0.0075 Tm 0.015 1.04 0.579 0.411 70.0 70.1 609 199.0 1.5 26.0
Embodiment 123 0.0075 Yb 0.015 1 0.579 0.410 39.0 39.4 610 2.0 1.3 29.8
Embodiment 124 0.0075 Lu 0.015 0.99 0.581 0.410 93.1 94.1 611 25.5 1.3 30.8
The fluor of embodiment 110 to 124 is with general formula (Ca 0.9775 'Eu 0.0075 'WR system 0.015) 2Si 5N 8Represented, the fluor of this embodiment 110 to 124 contains oxygen 1.0～1.6%.In embodiment 110 to 124, Eu concentration is 0.0075.Eu concentration is the mol ratio with respect to the volumetric molar concentration of Ca.In addition, activator WR uses rare earth element Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.The interpolation concentration of activator WR is 0.015.The interpolation concentration of WR system is the mol ratio with respect to the volumetric molar concentration of Ca.Comparative example 1 expression is not added activator WR and is only added the comparison of the fluor of Eu.
Also have, table 8 and Figure 14 are not to be the data of optimum value of the fluor that is activated of comparing embodiment 110 to 124, and are an embodiment.For example, as table 9, Figure 15 to shown in Figure 19, during with the changes such as use level of activator La, activator Eu, the fluor of the embodiment different with the use level of the activator La of table 8, its luminosity is the highest.Thus, by change use level of rare earth element and firing condition etc., promptly can make than the fluor of embodiment 110 to 124 and the higher fluor of its luminosity.
At first, the oxide compound with carbonitride, silicon nitride, europium sesquioxide, rare earth element mixes.The oxide compound of rare earth element wherein with WR is 2O 3Represented, but cerium, praseodymium, terbium are exception, and be respectively cerium oxide CeO 2, Praseodymium trioxide Pr 6O 11, terbium sesquioxide Tb 4O 7In embodiment 110 to 124, the CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3, rare earth element the mixture ratio (mol ratio) of oxide compound, can be adjusted to Ca: Si: Eu: rare earth element=1.955: 5: 0.015: 0.030.In this raw material, contain several ppm to Mn, Mg, Sr, Ba, Zn, B, Al, Cu, Cr and the Ni etc. of hundreds of ppm more than at least a kind.
The mixing above-claimed cpd also burns till.Firing condition is in ammonia atmosphere, be fed into the boron oxide crucible in, through about 5 hours and heat up lentamente, and, be cooled to room temperature lentamente through 5 hours with about 1350 ℃ and burnt till about 5 hours from room temperature.Substrate nitride phosphor (Ca after burning till 0.9775 'Eu 0.0075 'WR system 0.015) 2Si 5N 8
Embodiment 111 uses Y in activator WR.Be compared to the comparative example 1 that does not contain system of activator WR system, then form short persistence.By taking short persistence, promptly can be applied in the goods of indicating meter of being required short persistence etc.
Embodiment 112 uses La in activator WR system.Embodiment 112 is compared to comparative example 1, and its luminosity also increases by 11.4%.By the increase of luminosity, then be compared to comparative example 1 brighter fluor can be provided.In addition, quantum yield is also fabulous.And embodiment 112 is compared to comparative example 1 formation short persistence.
Embodiment 113 uses Ce in activator WR.Embodiment 113 is identical with embodiment 112, can reach the raising of luminosity.
Embodiment 114 uses Pr in activator WR.Embodiment 114 is compared to comparative example 1 and its luminosity also increases by 5.4%.By the increase of luminosity, then be compared to comparative example 1 brighter fluor can be provided.In addition, be compared to comparative example 1, then tone Y value does not change, and tone X then changes.By the variation of tone Y value, then be compared to comparative example 1 and also increase its red composition, and more reddish fluor can be provided.
Embodiment 115 uses Nd in activator WR.Embodiment 5 peak luminous wavelengths are for being offset to 621nm, and can increase red composition.Embodiment 115 is compared to comparative example 1 and forms steady persistence.
Embodiment 117, are Gd is used in activator WR.Embodiment 117 is identical with embodiment 112, can reach the raising of luminosity.
Embodiment 118, are Tb is used in activator WR.Embodiment 118 is identical with embodiment 112, can reach the raising of luminosity.Embodiment 118 quantum yielies are fabulous.
Embodiment 119, are Dy is used in activator WR.Embodiment 119 is identical with embodiment 112, can reach the raising of luminosity.
Embodiment 120, are Ho is used in activator WR.Embodiment 120 is identical with embodiment 112, can reach the raising of luminosity.Embodiment 120 is compared to comparative example 1 and forms short persistence.
Embodiment 121, are Er is used in activator WR.Embodiment 121 is identical with embodiment 112, can reach the raising of luminosity.Embodiment 121 is compared to comparative example 1 and forms short persistence.
Embodiment 124, are Lu is used in activator WR.Embodiment 124 is identical with embodiment 121, can reach the raising of luminosity.Embodiment 124 is compared to comparative example 1 and forms short persistence.
The temperature profile of the fluor of embodiment 110 to 124, each is all fabulous.Temperature profile is that expression is provided with this fluor when luminous element surperficial, and the composition of fluor does not change and shows the higher characteristics of luminescence, and temperature profile is higher, represents that then it is more stable.
The fluor of embodiment uses the crucible of boron nitride material, and burns till in ammonia atmosphere.Under this firing condition, since unlikely at etch stove and crucible, so sneaking into impurity, nothing burning till the situation of product.Though can use the crucible of boron nitride material, then cannot say not preferred when using molybdenum crucible.When using molybdenum crucible, must consider that the pincers of etch crucible contain in fluor, and produce the situation that the characteristics of luminescence descends.
So, the raising of the characteristics of luminescence can provide and carry out the luminous luminescent material of distincter white color system.In addition, the raising of the characteristics of luminescence is because can improve energy efficiency, so also can be to reach province's electrification.
Embodiment 125 to 133.
Embodiment 125 to 133 makes with substrate nitride phosphor Ca-Si-N:Eu the fluor that the interpolation concentration of the activator La of La is carried out various changes.Table 9 expression is substrate nitride phosphor Ca-Si-N:Eu, and the interpolation concentration of the activator La of La is carried out the chemical property and the physical property of fluor of the embodiment 125 to 133 of various changes.Figure 15 is that expression is measured substrate nitride phosphor Ca-Si-N:Eu, and the interpolation concentration of the activator La of La is carried out the figure of measurement result of luminosity of fluor of the embodiment 125 to 133 of various changes.Figure 16 be expression with substrate nitride phosphor Ca-Si-N:Eu, the interpolation concentration of the activator La of La is carried out the figure of luminescent spectrum of the embodiment 125 to 133 of various changes.Figure 17 be expression with substrate nitride phosphor Ca-Si-N:Eu, the interpolation concentration of the activator La of La is carried out the figure of reflection spectrum of the embodiment 125 to 133 of various changes.Figure 18 be expression with substrate nitride phosphor Ca-Si-N:Eu, the interpolation concentration of the activator La of La is carried out the figure of excitation spectrum of fluor of the embodiment 125 to 133 of various changes.Figure 19 A takes embodiment 128, and Figure 19 B is the photo of particle diameter of taking the fluor of embodiment 129.
Table 9
Eu concentration The interpolation concentration of La Tone x Tone y Luminosity (%) Quantum yield (%) Peak wavelength (nm) Median size (μ m) Temperature profile Amount
100℃ 200℃ 35℃ O (％) N (％)
Comparative example 1 0.0075 0 0.581 0.410 100 100 609 2.8 99.5 75.4 99.1 1.3 31.6
Embodiment 125 0.0075 0.005 0.581 0.410 101.8 101.7 609 3.0 98.5 74.3 98.7 1.2 31.6
Embodiment 126 0.0075 0.01 0.582 0.409 106.6 107.0 609 3.3 98.2 74.0 98.7 1.2 31.9
Embodiment 127 0.0075 0.015 0.583 0.409 111.4 111.9 609 3.6 98.8 75.3 99.8 1.3 31.2
Embodiment 128 0.0075 0.02 0.583 0.409 113.5 114.3 609 3.7 98.6 74.9 99.4 1.4 31.3
Embodiment 129 0.0075 0.03 0.582 0.410 108.4 105.9 608 3.6 99.0 77.4 98.7 1.4 30.9
Embodiment 130 0.0075 0.04 0.582 0.409 100.6 101.5 609 3.5 99.2 74.4 97.9 1.7 30.1
Embodiment 131 0.0075 0.06 0.582 0.410 96.7 98.0 609 3.6 98.0 70.6 98.6 1.9 29.6
Embodiment 132 0.0075 0.1 0.582 0.409 88.3 89.9 609 3.7 98.2 70.8 95.9 2.4 28.4
Embodiment 133 0.0075 0.2 0.582 0.409 64.6 66.6 610 3.9 98.1 69.9 98.1 3.6 26.5
This fluor is to be added with the general formula (Ca of Mn (1-0.0075-XEu 0.0075La X) 2Si 5N 8Represented.The fluor of this embodiment 125 to 133 contains 1.0～1.6% oxygen.In embodiment 125 to 133, Eu concentration is 0.0075.In embodiment 125 to 133, the interpolation concentration of making La changes over 0.005,0.01,0.015,0.02,0.03,0.04,0.06,0.1,0.2 fluor.Embodiment 125 to 133 is with La 2O 3Use is in raw material.Comparative example 1 is to represent not add activator La and the comparison of only adding the fluor of Eu.
Because embodiment 125 to 133 carries out the manufacturing process identical with embodiment 110 to 124, so omit locating of the identical formation of its experience.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
In embodiment 125 to 133, tone X and look and Y value are roughly the same.Peak wavelength is also roughly the same.With respect to this, improve luminosity along with the interpolation concentration that increases La lentamente.This is to consider the fusing assistant effect.The interpolation concentration of La is 0.02 o'clock, and the luminosity of its peak value descends.This is to think cause because of the concentration delustring.
In addition, twilight sunset is that each of embodiment 125 to 133 all forms shorter than comparative example 1.
In addition, temperature profile is that each of embodiment 125 to 133 is all fabulous.
The median size of embodiment 128 is 3.7 μ m, and the averageparticle of embodiment 20 is 3.6 μ m.With respect to this, the median size of comparative example 1 is 2.8 μ m.Cause therefore, median size is the raising that promptly can reach luminosity more than the 3.0 μ m.
＜embodiment 134 to 144 〉
Embodiment 134 to 144 makes with substrate nitride phosphor Ca-Si-N:Eu the fluor that the interpolation concentration of the activator Pr of Pr is carried out various changes.Table 10 expression is substrate nitride phosphor Ca-Si-N:Eu, and the interpolation concentration of the activator Pr of Pr is carried out the chemical property and the physical property of fluor of the embodiment 134 to 144 of various changes.
Table 10
Eu concentration The interpolation concentration of Pr Tone x Tone y Luminosity (%) Quantum yield (%) Peak wavelength (nm) Median size (μ m)
Comparative example 1 0.0075 0 0.581 0.410 100.0 100 609 2.8
Embodiment 134 0.0075 0.0025 0.582 0.410 103.3 102.8 609 2.7
Embodiment 135 0.0075 0.005 0.582 0.410 105.7 105.7 610 2.9
Embodiment 136 0.0075 0.0075 0.582 0.409 101.8 102.2 610 3.4
Embodiment 137 0.0075 0.01 0.582 0.409 98.8 99.3 610 3.3
Embodiment 138 0.0075 0.0125 0.582 0.409 96.7 97.2 610 3.4
Embodiment 139 0.0075 0.015 0.582 0.409 96.5 97.2 610 3.1
Embodiment 140 0.0075 0.0175 0.582 0.410 96.1 97.2 610 3.3
Embodiment 141 0.0075 0.02 0.582 0.409 93.4 94.3 610 3.1
Embodiment 142 0.0075 0.03 0.581 0.410 94.6 95.4 610 3.6
Embodiment 143 0.0075 0.06 0.581 0.410 84.4 86.1 610 3.5
Embodiment 144 0.0075 0.1 0.581 0.411 70.3 71.9 613 3.3
This fluor is to be added with the general formula (Ca of Mn (1-0.0075-XEu 0.0075Pr X) 2Si 5N 8And represent.The fluor of this embodiment 134 to 144 contains 1.0～1.6% oxygen.In embodiment 134 to 144, Eu concentration is 0.0075.In embodiment 134 to 144, the interpolation concentration of making Pr changes over 0.0025,0.005,0.0075,0.01,0.0125,0.015,0.0175,0.02,0.03,0.06,0.1 fluor.Embodiment 134 to 144 is with Pr 6O 11Use is at raw material.Comparative example 1 expression is not added activator Pr and is only added the comparison of the fluor of Eu.
Embodiment 134 to 144 is because carry out the manufacturing process identical with embodiment 110 to 124, so omit locating of the identical formation of its experience.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
In embodiment 134 to 144, tone X and color harmony Y value are roughly the same.Peak wavelength is also roughly the same.To this situation, the interpolation concentration along with increasing Pr lentamente promptly can improve luminosity.This is the cause of sensitizing effect.During the interpolation concentration 0.05 of Pr, the luminosity of its peak value promptly descends.This is the cause of concentration delustring.The raising of embodiment 139 its luminosity of may observe.
In addition, each of twilight sunset embodiment 125 to 133 all forms shorter than comparative example 1.
Each of temperature profile embodiment 134 to 144 is all fabulous.For example, be 68.1% when being 99.2%, 200 ℃ during 100 ℃ of the temperature profiles of embodiment 135, be 74.8%, all fabulous when being 98.6%, 200 ℃ during 100 ℃ of the temperature profiles of embodiment 139.
In embodiment 136～144, generating median size is the above fluor of 3.0 μ m, and shows high luminescent spectrum.
＜embodiment 145 to 148 〉
Embodiment 145 to 148 makes substrate nitride phosphor Ca-Si-N:Eu, and the Eu concentration of Pr is carried out the fluor of various changes.Table 11 be expression with substrate nitride phosphor Ca-Si-N:Eu, the concentration of Pr is carried out the chemical property and the physical property of fluor of the embodiment 145 to 148 of various changes.
Table 11
Eu concentration The interpolation concentration of Pr Tone x Tone y Luminosity (%) Quantum yield (%) Peak wavelength (nm)
Comparative example 1 0.0075 0 0.581 0.410 100.0 100 609
Embodiment 145 0.0075 0.005 0.582 0.410 105.7 105.7 610
Embodiment 146 0.015 0.005 0.584 0.407 112.3 113.9 609
Embodiment 147 0.03 0.005 0.588 0.403 117.3 123.9 610
Embodiment 148 0.06 0.005 0.590 0.401 109.2 119.6 612
This fluor is to be added with the general formula (Ca of Mn (1-Y-0.005)Eu YPr 0.005) 2Si 5N 8And represent.Fluor at this embodiment 145 to 148 contains 1.0～1.6% oxygen.In embodiment 145 to 148, the interpolation concentration of Pr is 0.005.In embodiment 145 to 148, make Eu concentration is changed over 0.0075,0.0015,0.03,0.06 fluor.Embodiment 145 to 148 is with Pr 6O 11Use is at raw material.
Embodiment 145 to 148 is owing to carry out the manufacturing process identical with embodiment 1 to 15, so omit locating of the identical formation of its experience, in this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
In embodiment 145 to 148, tone X and color harmony Y value are because of Eu concentration difference to some extent.Red composition also increases along with the increase of Eu concentration, more can provide reddish fluor.In addition, improve its luminosity along with the increase of Eu concentration.Particularly luminosity embodiment 146 and 147 each is all high.This is the cause of sensitizing effect.Temperature profile is that each of embodiment 145 to 148 is all fabulous.
Embodiment 149 to 155
Embodiment 149 to 155 makes with substrate nitride phosphor Sr-Ca-Si-N:Eu the fluor that the Sr of La and the mixture ratio of Ca carry out various changes.Table 12 expression is substrate nitride phosphor Sr-Ca-Si-N:Eu, and the interpolation concentration of the activator La of La is carried out the chemical property and the physical property of fluor of the embodiment 149 to 155 of various changes.
Table 12
Sr/Ca Eu concentration The interpolation concentration of La Tone x Tone y Luminosity (%) Quantum yield (%) Peak wavelength (nm)
Comparative example 1 0/10 0.0075 0 0.581 0.410 100.0 100 609
Embodiment 149 0/10 0.0075 0.02 0.583 0.409 113.5 114.3 609
Embodiment 150 3/7 0.0075 0.02 0.595 0.395 63.7 76.3 624
Embodiment 151 4/6 0.0075 0.02 0.680 0.382 64.0 85.9 627
Embodiment 152 5/5 0.0075 0.02 0.618 0.372 67.0 100.2 634
Embodiment 153 6/4 0.0075 0.02 0.615 0.374 66.1 94.7 633
Embodiment 154 7/3 0.0075 0.02 0.612 0.378 70.9 93.4 626
Embodiment 155 10/0 0.0075 0.02 0.604 0.387 89.2 95.4 618
This fluor is with general formula (Sr TCa (1-T-0.0075-0.005)Eu 0.0075La 0.005) 2Si 5N 8And represent.Fluor at this embodiment 149 to 155 contains 1.0～2.0% oxygen.In embodiment 149 to 155, Eu concentration 0.0075, the interpolation concentration 0.02 of La.Embodiment 149 to 155 is with La 6O 11Use is at raw material.Comparative example 1 expression interpolation Sr: Ca=0: 10, activator La and only add the comparison of the fluor of Eu.
Embodiment 149 to 155 is because carry out the manufacturing process identical with embodiment 110 to 124, so omit locating of the identical formation of its experience.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
The fluor of embodiment 149 to 155 is the fluor of the mixed crystal of Sr and Ca.The fluor of the mixed crystal of Sr and Ca changes tone, peak wavelength by the mixture ratio that changes Sr and Ca.Peak wavelength is offset to long wavelength side along with the increase of Sr.Sr: Ca=5: 5 o'clock, the extremely long wavelength side of peak wavelength shift.Promptly can be manufactured on thus than Sr-Ca-Si-N:Eu, WR is that more long wavelength side has the fluor of the reddish warm colour system of peak wavelength.In embodiment 149 to 155, tone X and tone Y value change according to the mixture ratio of Sr and Ca.Can make the fluor of tone thus with expectation.For example, mixed C a-Si-N:Eu, the fluor of La and Sr-Ca-Si-O-N:Eu, the light-emitting device of La can be provided in the light-emitting device of the tone of the expectation that has peak wavelength in the scope of 609nm to 634nm.Temperature profile is that each of embodiment 149 to 155 is all fine.
Embodiment 156 to 160.
Embodiment 156 to 160 makes with substrate nitride phosphor Ca-Si-N:Eu the fluor that the interpolation concentration of the activator Tb of Tb is carried out various changes.Table 13 expression is substrate nitride phosphor Ca-Si-N:Eu, and the interpolation concentration of the activator Tb of Tb is carried out the chemical property and the physical property of fluor of the embodiment 156 to 160 of various changes.
Table 13
Eu concentration The interpolation concentration of Tb Tone x Tone y Luminosity (%) Quantum yield (%) Peak wavelength (nm)
Comparative example 1 0.0075 0 0.581 0.410 100.0 100.0 609
Embodiment 156 0.0075 0.015 0.582 0.409 99.1 100.4 610
Embodiment 157 0.0075 0.03 0.579 0.412 82.0 81.7 609
Embodiment 158 0.0075 0.06 0.579 0.412 77.8 78.0 610
Embodiment 159 0.0075 0.1 0.578 0.412 66.1 66.4 609
Embodiment 160 0.0075 0.2 0.576 0.414 43.2 43.7 609
This fluor is to be added with the general formula (Ca of Mn (1-0.0075-X)Eu 0.0075Tb X) 2Si 5N 8And represent.Fluor at this embodiment 156 to 160 contains 1.0～2.0% oxygen.In embodiment 156 to 160, Eu concentration 0.0075.In embodiment 156 to 160, the interpolation concentration of making Tb changes over 0.015,0.03,0.06,0.1,0.2 fluor.Embodiment 156 to 160 uses Tb 4O 11Comparison at raw material.
Embodiment 156 to 160, because carry out the manufacturing process identical with embodiment 110 to 124, so omit locating of the identical formation of its experience, in this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.Each is all good for the temperature profile of embodiment 156 to 160.For example, the temperature profile of embodiment 156 is 77.0% when being 98.9%, 200 ℃ in the time of 100 ℃, and the temperature profile of embodiment 159 is 69.4% and very preferred when being 97.2%, 200 ℃ in the time of 100 ℃.
Embodiment 161 to 165.
Embodiment 161 to 165 makes with substrate nitride phosphor Ca-Si-N:Eu the fluor that the interpolation concentration of the activator Nd of Tb is carried out various changes.Table 14 expression is substrate nitride phosphor Ca-Si-N:Eu, among the Nd the interpolation concentration of activator Nd carry out the chemical property and the physical property of fluor of the embodiment 161 to 165 of various changes.
Table 14
Eu concentration The interpolation concentration of Nd Tone x Tone y Luminosity (%) Quantum yield (%) Peak wavelength (nm)
Comparative example 1 0.0075 0 0.581 0.410 100.0 100.0 609
Embodiment 161 0.0075 0.015 0.582 0.406 87.4 91.2 621
Embodiment 162 0.0075 0.03 0.580 0.412 68.8 71.7 621
Embodiment 163 0.0075 0.06 0.579 0.412 59.5 63.1 622
Embodiment 164 0.0075 0.1 0.578 0.413 48.9 53.4 623
Embodiment 165 0.0075 0.2 0.572 0.416 26.7 30.1 624
This fluor is to be added with the general formula (Ca of Mn (1-0.0075-X)Eu 0.0075Nd X) 2Si 5N 8And represent.Contain 1.0～2.0% oxygen at this embodiment 161 to 165.In embodiment 161 to 165, Eu concentration 0.0075.In embodiment 161 to 165, the interpolation concentration of making Nd changes over 0.015,0.03,0.06,0.1,0.2 fluor.Embodiment 161 to 165 uses Nd 2O 3Use is at raw material.Comparative example 1 expression is not added activator Nd and is only added the comparison of the fluor of Eu.
Embodiment 161 to 165 is because carry out the manufacturing process identical with embodiment 1 to 15, so omit locating of the identical formation of its experience, in this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
In embodiment 161 to 165, along with the increase of the interpolation concentration of Nd and tone X and tone Y value are changed.Along with the increase of the interpolation concentration of Nd, and tone X value descends, the rising of tone Y value.Be compared to embodiment 163 therefrom, then form slightly yellowish red color.On the other hand, peak wavelength is offset to long wavelength side along with the increase of the interpolation concentration of Nd.Make twilight sunset elongated by adding Nd.Each of temperature profile embodiment 161 to 165 is all fabulous.For example, the temperature profile of embodiment 161 is 77.6% when being 99.7%, 200 ℃ in the time of 100 ℃, and the temperature profile of embodiment 164 is 76.7% when being 99.6%, 200 ℃ in the time of 100 ℃, is preferred.
Embodiment 166.
The light-emitting device of embodiments of the invention 166 is to use the fluor of embodiments of the invention 135 and the light-emitting device of the Class1 that constitutes, and for can carry out the luminous white color system light-emitting device of reddish white color system.
Use is to use the fluor of mix embodiment 135 and the yttrium that is activated with cerium at the fluor 11 of the light-emitting device of present embodiment 166. and aluminum oxide is the fluor of fluorescent substance (Y-Gd-Al-O:Ce).Embodiment 135Ca-Si-On:Eu, the fluor of Pr.The light-emitting device of making does not contain the fluor of embodiment 26, and only contains the yttrium that is activated with cerium as a comparison. gadolinium. and aluminum oxide is a fluorescent substance and as fluor.The light-emitting device of present embodiment 166 and comparative example uses (Y 0.8Gd 0.2) 3Al 5O 12: the fluor of Ce.Also promptly, the light-emitting device of comparative example carries out luminous with the combination of blue based light-emitting device and fluor (Y-Gd-Al-O:Ce).
The weight ratio of the fluor 11 of the light-emitting device of embodiment 166, coating member: the fluor of fluor (Y-Gd-Al-O:Ce): embodiment 26=10: 3.8: 0.6.On the other hand, the weight ratio of the fluor of the light-emitting device of comparative example is with coating member: the weight ratio of fluor (Y-Gd-Al-O:Ce)=10: 36 and mixing.
With the light-emitting device 1 of present embodiment 166 with only use the luminous dress straight 2 of comparative example of the fluor of blue based light-emitting device and Y-Gd-Al-O:Ce to compare.The light-emitting device of present embodiment 166 and the light-emitting device of comparative example relatively, though tone for roughly not changing, color developing is improved.It is inadequate that number R9 is estimated in the light-emitting device 2 special colour developings of comparative example, but the light-emitting device 1R9 of embodiment 166 is for improving.The value that number R9 measures the chroma offset of the higher redness of chroma is estimated in special colour developing.In addition, other special colour developing is estimated number R8, R10 etc. and is also improved the value that becomes more near 100%.Lamp efficiency is represented higher numerical value.
Embodiment 167.
The light-emitting device of embodiments of the invention 167 is to use the fluor of embodiment 154 and the light-emitting device of the bulb look that constitutes.The light-emitting device of embodiment 167 is the light-emitting device of Class1, and the formation of construction drawing 1.Figure 20 is the figure of tristimulus coordinates of the light-emitting device 3 of expression present embodiment 167.
In the light-emitting device of present embodiment 167, fluor 11 uses the fluor of mix embodiment 154 and the yttrium that is activated with cerium. gallium. and aluminum oxide is the fluor of fluorescent substance (Y-Ga-Al-O:Ce).More specifically, the light-emitting device shi of embodiment 167 uses Y 3(Al 0.8Ga 0.2) 5O 12: the fluor of the composition of Ce, Y 3(Al 0.8Ga 0.2) 5O 12: the fluor of the composition of Ce, when exciting with the light of wavelength Ex=460nm, then the peak wavelength of luminescent spectrum is 530～540nm.Similarly, the peak wavelength 625nm of the fluor of embodiment 158.
The weight ratio of this type of fluor 11 is, with coating member: the weight ratio of the fluor of fluor (Y-Ga-Al-O:Ce): embodiment 158=10: 4.0: 1.08 and mixing.
Use and so to handle and the light-emitting device of the embodiment 167 of blended fluor, carry out the luminous of bulb look.During according to Figure 20 of tristimulus coordinates of the light-emitting device 3 of expression embodiment 167, then tone X and tone Y are positioned at the luminous zone of white color system of warm colour system.The special colour developing of the light-emitting device 3 of embodiment 167 is estimated number R9 and is also improved 60% and color developing.Peak wavelength also is positioned near the 620nm and red area, and can obtain the white color system light-emitting device of bulb look.Color temperature, color developing Ra might as well, and have the characteristics of luminescence near the bulb look.In addition, the light-emitting device 3 of embodiment 167 has the high characteristics of luminescence of 19～221m/W.
Embodiment 168.
The light-emitting device of embodiment 168 be to use luminescence peak be have blue region 460nm the InGa semiconductor layer luminous element 101 and as the luminous element of the type 2 of luminescent layer, and use the fluor of embodiment 1.
In the light-emitting device of this embodiment 168, light with luminescent spectrum of the blueness luminous with luminous element 101, be the luminescent spectrum of the indirect that reflects with reflector and self-emission device 101 and the luminescent spectrum that directly penetrates, for being radiated at fluor 108, and form the luminous fluor of white color system.By mixing on fluor 108 of the present invention: green is light-emitting fluophor SrAl 2O 4: Eu, Y 2SiO 5: Ce, Tb, MgAl 11O 19: Ce, Tb, Sr 7Al 12O 25: Eu, (Mg, Ca, Sr, Ba in more than at least 1) Ga 2S 4: Eu, blueness are light-emitting fluophor Sr 5(PO 4) 3Cl:Eu, (SrCaBa) 5(PO 4) 3Cl:Eu, (BaCa) 5(PO 4) 3Cl:Eu, (Mg, Ca, Sr, Ba in more than at least 1) 2B 5O 9Cl:Eu, Mn, (Mg, Ca, Sr, Ba in more than at least 1) (PO 4) 6Cl 2: Eu, Mn, red colour system light-emitting fluophor Y 2O 2S:Eu, La 2O 2S:Eu, Y 2O 3: Eu, Ga 2O 2S:Eu etc., the luminescent spectrum that can obtain to expect.
Use the light-emitting device as above handle and to constitute and when making the White LED electric light, can obtain 99% yield rate.So, the light-emitting device of embodiment 168 can productivity be produced admirably, and reliability is higher and can reduce the phenomenon of mottle.
Embodiment 169.
The light-emitting device of embodiments of the invention 169 is light-emitting devices of the type 3 of cabinet-type, and uses the fluor of embodiment 152 and constitute.
So and the light-emitting device of the embodiment 360 that constitutes, the part of self-emission device 10 and the light of emitting is for by wall 16 time, and the fluor by embodiment 152 imposes wavelength conversion.The light of such wavelength conversion and the light that does not carry out the blueness system of wavelength conversion according to fluor mix, its result, the light of white color system from the surface emitting of wall 16 to outside.
＜relate to the embodiment 170～223 of embodiment 4 〉
Embodiment 170 to 176.
Chemical property and the physical property of the embodiment 170 to 176 of table 15 expression fluor of the present invention.
In addition, Figure 22 to 24 is figure of the characteristics of luminescence of the fluor of expression embodiment 173.
Figure 22 is the figure of the luminescent spectrum of expression when exciting the fluor of embodiment 173 with Ex=460nm.Figure 23 is the figure of excitation spectrum of the fluor of expression embodiment 173.Figure 24 is the figure of reflection spectrum of the fluor of expression embodiment 173.Figure 25 is the figure of the luminescent spectrum of expression when exciting the fluor of embodiment 170 to 176 with Ex=460nm.
Table 15
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Sr/Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
170 9/1 1.746/0.194/ 5/0.06 0.015 0.03 0.616 0.375 100.0 100.0 624 99.4 92.7
171 7/3 1.358/0.582/ 5/0.06 0.015 0.03 0.629 0.362 95.3 126.9 639 104.5 100.1
172 6/4 1.164/0.776/ 5/0.06 0.015 0.03 0.635 0.356 103.4 157.9 643 106.0 99.6
173 5/5 0.97/0.97/5/ 0.06 0.015 0.03 0.631 0.359 111.2 167.7 644 105.9 97.9
174 4/6 0.776/1.164/ 5/0.06 0.015 0.03 0.622 0.369 118.1 160.2 642 101.0 93.1
175 3/7 0.582/1.358/ 5/0.06 0.015 0.03 0.610 0.381 123.7 146.5 636 100.1 93.8
176 1/9 0.194/1.746/ 5/0.06 0.015 0.03 0.587 0.405 170.3 138.5 609 90.7 51.2
Embodiment 170 to 176 checks with the chemical property of the represented fluor of the Sr-Ca-Si-N:Eu that adds Mn of the present invention or the result of physical property.The raw material ratio of mixture of table 15 is represented raw material with mol ratio.This fluor is to be added with the general formula Sr of Mn XCa (1.94-X)Eu 0.06Si 5N 8(0≤X≤1.94) and represent, or use the material that contains micro amount of oxygen.In embodiment 170 to 176, Eu concentration is 0.03.Eu concentration is the mol ratio to the volumetric molar concentration of Sr-Ca.In addition, to Si 5 and the addition of Mn is 0.015.Embodiment 170 to 176 is the results that suitably change the ratio of Sr concentration and Ca concentration.
At first, strontium nitride, CaCl2, silicon nitride, europium sesquioxide are mixed.In embodiment 170, the strontium nitride Sr of raw material 3N 2, CaCl2 Ca 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Mixture ratio (mol ratio), be adjusted into Sr: Ca: Si: Eu=X: 1.94-X: 5: 0.06.
Mn adds 0.015 with mol ratio.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Mix above-claimed cpd and burn till.Firing condition is fed into boron nitride crucible in ammonia atmosphere, approximately heated up lentamente from room temperature through 5 hours, and with about 1350 ℃ and carry out 5 hours burn till, through being cooled to room temperature lentamente in 5 hours.Sr after burning till XCa (1.94-X)Eu 0.06Si 5N 8In (0≤X≤1.94), Mn extant number ppm～tens of ppm degree.
The mol ratio of the Sr of embodiment 170: Ca is 9: 1.As 100%, quantum yield makes 100% with the luminance of the silicon nitride fluor of embodiment 170, and is the luminous efficiency that benchmark is formulateeed and implemented example 171 to 176 during with this cooperation ratio.When the cooperation ratio that increases with respect to the Ca of Sr, the mol ratio of Sr: Ca is 7: 3 o'clock, and the quantum yield of silicon nitride fluor is 126.9%, and peak wavelength is 639nm.The raising, particularly peak wavelength that promptly can reach quantum yield thus are for being offset to more long wavelength side.And then when increasing cooperation ratio with respect to the Ca of Sr, the mol ratio of Sr: Ca is 5: 5, and also promptly 1: 1 o'clock, the luminosity of silicon nitride fluor was 111.2%, and quantum yield is 167.7%, and peak wavelength is 644nm.According to this result, then be compared to Sr: Ca=9: more can reach the raising of the luminous efficiency of luminosity, quantum yield etc. at 1 o'clock.Particularly peak wavelength is because be offset to more long wavelength side, so can make the slightly fluor of red color tone.In addition, temperature profile is also highly desirable, and then when the cooperation ratio that increases with respect to the Ca of Sr, then peak wavelength shift is to short wavelength side.During this situation also can so that luminosity, quantum yield do not descend and can obtain the fabulous characteristics of luminescence.Particularly, because Sr is a high price than Ca, so, promptly can reach the attenuating manufacturing cost by increasing the cooperation ratio of Ca.
By the fluor that suitably makes up the foregoing description 170 to 176 and the Sr-Si-N:Eu that adds Mn described later, add the Ca-Si-N:Eu of Mn or add Mn Sr-Ca-Si-O-N:Eu, add Mn Sr-Si-O-N:Eu, add the Ca-Si-O-N:Eu of Mn, promptly can make the fluor of peak wavelength with expectation.Because this type of has roughly the same composition, and does not have mutual buffered situation, so have the fabulous characteristics of luminescence.
The fluor of embodiment uses the crucible of boron nitride material, and burns till in ammonia atmosphere.Under this firing condition,,, use molybdenum crucible also preferred not to the utmost though can use the crucible of boron nitride material because the phenomenon of no etch stove and crucible is not sneaked into impurity to burning till product so have.The molybdenum that must consider the etch crucible when using molybdenum crucible is for containing in fluor, and the decline of the generation characteristics of luminescence.
So, the raising of the characteristics of luminescence can provide and carry out the luminous luminescent material of distincter white color system.In addition, the raising of the characteristics of luminescence is because improve energy efficiency, so also can be to reach province's electrification.
In addition, temperature profile is shown in and this fluor is set when luminous element surperficial, the composition of fluor is not changed can represent the higher characteristics of luminescence, and the high more expression of temperature profile is stable more.
Embodiment 177 to 180
Chemical property and the physical property of the embodiment 177 to 180 of table 16 expression fluor of the present invention.Figure 26 is the figure of the luminescent spectrum of expression when exciting the firefly of embodiment 177,178,180,181,182,184,190,191,193 to give birth to body with Ex=460nm.
Embodiment 177 to 180 is the chemical property during with the Eu change in concentration of the represented fluor of the Sr-Ca-Si-N:Eu that adds Mn of the present invention or the result of study of physical property.This fluor is to be added with the general formula Sr of Mn XCa (2-T-X)Eu TSi 5N 8(0≤X≤2) and represent, or use the oxygen that contains trace.The cooperation ratio of the raw material of Sr and Ca is Sr: Ca=X: 2-T-X=7: 3.The blending ratio of Eu is for using T=0.01,0.03,0.06 and 0.12.Eu concentration during this situation is 0.005,0.015,0.03,0.06.The concentration of Eu is the mol ratio to the volumetric molar concentration of Sr-Ca.In addition, to Si 5 and the addition of Mn is 0.015.
Table 16
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Sr/Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
177 7/3 1.393/0.597/ 5/0.01 0.015 0.005 0.605 0.384 100.0 100.0 624 105.1 103.4
178 7/3 1.379/0.591/ 5/0.03 0.015 0.015 0.619 0.370 135.0 162.0 631 104.1 104
179 7/3 1.358/0.582/ 5/0.06 0.015 0.03 0.631 0.360 139.5 199.2 637 106 103.7
180 7/3 1.316/0.564/ 5/0.12 0.015 0.06 0.640 0.349 124.5 219.1 646 108.5 103.1
Embodiment 177 to 180, because carry out the manufacturing process identical with embodiment 170 to 176, so omit locating of the identical formation of its experience, in this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Fluor with embodiment 177 is that benchmark is represented luminous efficiency.When Eu concentration is 0.03 embodiment 179, can observe the raising of luminosity.Eu concentration more after a little while, then can't carry out fully luminous, in addition, when Eu concentration is too much, then with concentration delustring or Sr 2N 3, Ca 2N 3React, and owing to make and the different composition of substrate nitride phosphor that forms purpose, so produce the situation that luminous efficiency descends.Embodiment 180 its quantum yielies are for most preferably.On the other hand, along with the increase of Eu concentration peak wavelength shift to long wavelength side.Though this principle is uncertain, can be considered according to Mn promotes Sr along with the increase of Eu concentration 2N 3And Ca 2N 3Diffusion, can promote the mixed crystal of Sr and Ca, and peak wavelength shift is to long wavelength side.Each of temperature profile embodiment 177 to 180 is all fabulous.
Embodiment 181 to 189.
Chemical property and the physical property of the embodiment 181 to 189 of table 17 expression fluor of the present invention.
Table 17
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Sr/Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
181 5/5 0.99/0.99/5/ 0.01 0.015 0.005 0.611 0.378 100.0 100.0 628 104.2 98.6
182 5/5 0.985/0.985/ 5/0.03 0.015 0.015 0.623 0.367 127.7 148.5 637 105.1 99.6
183 5/5 0.97/0.97/5/ 0.06 0.015 0.03 0.631 0.359 132.3 178.1 644 105.9 97.9
184 5/5 0.94/0.94/5/ 0.12 0.015 0.06 0.644 0.345 111.8 195.8 656 99 81
185 5/5 0.94/0.94/5/ 0.12 0.015 0.06 0.636 0.353 30.3 47.1 658 100.1 92.3
186 5/5 0.9/0.9/5/ 0.2 0.015 0.1 0.648 0.342 80.5 156.2 663 108.3 83.9
187 5/5 0.85/0.85/5/ 0.3 0.015 0.15 0.653 0.337 83.6 185.4 667 111.8 78.2
188 5/5 0.8/0.8/5/ 0.4 0.015 0.2 0.655 0.335 74.4 179.2 668 112 70.3
189 5/5 0.7/0.7/5/ 0.6 0.015 0.3 0.657 0.333 58.5 152.2 670 111.3 56.7
Embodiment 181 to 189 checks the chemical property with the Eu change in concentration of the represented fluor of the Sr-Ca-Si-N:Eu that adds Mn of the present invention time the or the result of study of physical property.This fluor is to be added with the general formula Sr of Mn XCa (2-T-X)Eu TSi 5N 8(0≤X≤2) and represent, or use the material of the oxygen that contains trace.The cooperation ratio Sr of the raw material of Sr and Ca: Ca=X: 2-T-X=5: 5.The cooperation ratio of the Eu of embodiment 181 to 184 is used T=0.01,0.03,0.06,0.12.Eu concentration during this situation is 0.005,0.015,0.03,0.06.The concentration of Eu is to the mol ratio of Sr-Ca.The cooperation ratio of the Eu of embodiment 185 to 189 is used T=0.12,0.2,0.3,0.4,0.6.Eu concentration 0.06,0.1,0.15,0.2,0.3 during this situation.The addition of the Mn of embodiment 181 to 189 to Si 5 and the addition of Mn is 0.015.
Embodiment 181 to 189, because carry out the manufacturing process identical with embodiment 170 to 176, so omit locating of the identical formation of its experience, in this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Fluor with embodiment 181 is that benchmark is represented luminous efficiency.When Eu concentration is 0.03 embodiment 183, can observe the raising of luminosity.Eu concentration more after a little while, then can't carry out fully luminous, in addition, when Eu concentration is too much, then with concentration delustring or Sr 2N 3, Ca 2N 3React, and owing to make the material of the composition different with the substrate nitride phosphor that forms purpose, so produce the situation that luminous efficiency descends.Its quantum yield is for the most desirable among the embodiment 184.Though embodiment 185 to 189 produces the phenomenon that luminosity descend, because it uses commercially available raw material, so be regarded as containing impurity in this raw material and the decline that produces the characteristics of luminescence.Among embodiment 181 to 185, the embodiment 185 to 189, make peak wavelength move to long wavelength side along with increasing Eu concentration.Though this raw material is uncertain, can be considered according to Mn promotes Sr along with the increase of Eu concentration 2N 3, Ca 2N 3Diffusion, and more can promote the mixed crystal of Sr and Ca, and peak wavelength shift is to long wavelength side.Temperature profile is that each of embodiment 181 to 189 is all fine.
Embodiment 190 to 193.
Chemical property and the physical property of the embodiment 190 to 193 of table 18 expression fluor of the present invention.
Table 18
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Sr/Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
190 3/7 0.597/1.393/ 5/0.01 0.015 0.005 0.597 0.392 100.0 100.0 621 101.5 89.6
191 3/7 0.591/1.379/ 5/0.03 0.015 0.015 0.598 0.392 110.3 113.5 626 98.2 77.5
192 3/7 0.582/1.358/ 5/0.06 0.015 0.03 0.610 0.381 141.4 175.8 636 100.1 93.8
193 3/7 0.564/1.368/ 5/0.12 0.0.15 0.06 0.604 0.387 95.6 113.0 635 91.6 55.2
Embodiment 190 to 193 checks the chemical property with the Eu change in concentration of the represented fluor of the Sr-Ca-Si-N:Eu that adds Mn of the present invention time the or the result of study of physical property.This fluor is to be added with the general formula Sr of Mn XCa (2-T-X)Eu TSi 5N 8(0≤X≤2) and represent, or use the oxygen that contains trace.The cooperation ratio Sr of the raw material of Sr and Ca: Ca=X: 2-T-X=3: 7.The cooperation ratio of the Eu of embodiment 190 to 193 is used T=0.01,0.03,0.06,0.12.Eu concentration during this situation is 0.005,0.015,0.03,0.06.The concentration of Eu is the mol ratio to Sr-Ca.The addition of the Mn of embodiment 190 to 193 to Si 5 and the addition of Mn is 0.015.
Embodiment 190 to 193 is because carry out the manufacturing process identical with embodiment 170 to 176, so omit locating of the identical formation of its experience, in this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Fluor with embodiment 190 is that benchmark is represented luminous efficiency.Identical to the embodiment of table 17 with table 15, during Eu concentration 0.03, embodiment 192 can observe the raising of its luminosity among the embodiment 190 to 193.With regard to the viewpoint of luminosity, Eu concentration is 0.03 o'clock, is regarded as making best phosphor body.In addition, embodiment 192 luminosity and quantum yield are most preferably.In embodiment 190 to 193, peak wavelength shift is to long wavelength side along with increasing Eu concentration.Temperature profile is that each of embodiment 190 to 193 is all fine.
Embodiment 194 to 201.
Chemical property and the physical property of the embodiment 194 to 201 of table 19 expression fluor of the present invention.
Table 19
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
194 0/10 1.985/5 /0.015 - 0.0075 0.581 0.411 100.0 100.0 609 99.5 78.9
195 0/10 1.985/5 /0.015 0.0025 0.0075 0.582 0.410 102.4 103.1 609 96.3 80.3
196 0/10 1.985/5 0.005 0.0075 0.581 0.410 101.5 102.0 609 99 76.9
/0.015
197 0/10 1.985/5 /0.015 0.0075 0.0075 0.581 0.410 113.6 108.3 609 100.1 76.9
198 0/10 1.985/5 /0.015 0.015 0.0075 0.583 0.409 115.3 117.4 609 100.1 76.9
199 0/10 1.985/5 /0.015 0.03 0.0075 0.581 0.411 93.2 93.8 609 98.5 73.6
200 0/10 1.985/5 /0.015 0.05 0.0075 0.578 0.413 68.7 68.8 609 89.5 55.8
201 0/10 1.985/5 /0.015 0.1 0.0075 0.572 0.418 32.2 31.9 609 71.9 30.8
Embodiment 194 to 201 be the addition of the Eu concentration of the fluor represented with Ca-Si-N:Eu of the present invention when changing chemical property or the check result of physical property.The raw material ratio of mixture of table 19 is to represent raw material with mol ratio.So and the fluor of making, to be added with the general formula Ca of Mn (2-T)Eu TSi 5N 8Or contain the trace oxygen formation and represent.Be not shown in embodiment 194 with what add Mn.It is 0.005,0.01,0.015,0.03,0.06,0.1 and 0.2 that the fluor of embodiment 195 to 201 uses the addition of Mn.Eu concentration during this situation is 0.0025,0.005,0.0075,0.015,0.03,0.05 and 0.1, and Mn concentration is the mol ratio to the volumetric molar concentration of Ca.The concentration fixed of Eu is 0.0075.
Embodiment 194 to 201, because carry out the manufacturing process identical with embodiment 170 to 176, so omit locating of the identical formation of its experience.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Fluor with the Mn that do not add embodiment 194 is that benchmark is represented luminous efficiency.Eu concentration is 0.075 embodiment 197 and Mn concentration when being 0.015 embodiment 198, can observe the raising of luminosity.This is to work as Mn concentration for more after a little while, then can't carry out the diffusion of raw material fully, and can't carry out the growth of particle.On the other hand, when Mn concentration was too much, then the Mn relative was regarded as hindering the composition of Ca-Si-N:Eu and forms and the reason of crystalline growth.Embodiment 195 to 198 quantum yielies are preferred.Even the temperature profile of embodiment 194 to 200 is when changing the addition of Mn and also very preferred.Even also be fixing during the addition of peak wavelength change Mn.
Embodiment 202 to 204.
Chemical property and the physical property of the embodiment 202 to 204 of table 20 expression fluor of the present invention.
Table 20
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
202 0/10 1.97/5 /0.03 - 0.015 0.586 0.406 100.0 100.0 609 93.8 66
203 0/10 1.97/5 /0.03 100ppm 0.015 0.585 0.406 100.5 100.3 610 97 69.7
204 0/10 1.97/5 /0.03 500ppm 0.015 0.588 0.403 103.5 103.1 610 96.5 66.2
Embodiment 202 to 204 be the addition with the Mn of the represented fluor of Ca-Si-N:Eu of the present invention when changing chemical property or the result of study of physical property.The raw material ratio of mixture of table 20 is represented raw material with mol ratio.Eu concentration be 0.015 o'clock then for fixing.So and the fluor of making, to be added with the general formula Ca of Mn (2-T)Eu TSi 5N 8Or contain the trace oxygen form and represent.Be not shown in embodiment 202 with adding Mn person.Use the addition of Mn in the fluor of embodiment 202 to 204, the gross weight of raw material is used 100ppm and 500ppm.
Embodiment 202 to 204 is because carry out the manufacturing process identical with embodiment 170 to 176, so omit locating of the identical formation of its experience.At first, CaCl2, silicon nitride, europium sesquioxide are mixed.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Fluor with the Mn that do not add embodiment 202 is that benchmark is represented luminous efficiency.The addition of Mn is each of 100ppm and 500ppm, all can observe the raising of its luminosity and quantum yield.In addition, also reach the raising of temperature profile.When such addition is a small amount of, and also can be with the raising of the characteristics of luminescence that reaches luminosity, quantum yield, temperature profile etc.
Embodiment 205 and 206.
The embodiment 205 of table 21 expression fluor of the present invention and 206 chemical property and physical property.Figure 27 A is embodiment 205, and Figure 27 B is the photo of particle diameter of the shooting fluor of embodiment 206.
Table 21
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
205 0/10 1.96/5 /0.04 - 0.02 0.589 0.403 100.0 100.0 609 95.9 65.5
206 0/10 0.96/5 /0.04 0.02 0.02 0.592 0.401 109.5 111.8 609 92.3 56.1
Embodiment 205 and 206 be the addition of the Mn of the fluor represented with Ca-Si-N:Eu of the present invention when changing chemical property or the result of study of physical property.The raw material ratio of mixture of table 21 is represented raw material with mol ratio.So and the fluor of making, to be added with the general formula Ca of Mn (2-T)Eu TSi 5N 8Or contain the trace oxygen form and represent.Be not shown in embodiment 205 with adding Mn person.The addition of the Mn that the fluor use of embodiment 206 is 0.04 mole.Mn concentration during this situation is 0.02, and Mn concentration is the mol ratio to the volumetric molar concentration of Ca.Eu concentration, 0.02 for fixing.
Embodiment 205 with 206 because carry out the manufacturing process identical, so omit locating of the identical formation of its experience with embodiment 170 to 176.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Fluor with the Mn that do not add embodiment 205 is that benchmark is represented luminous efficiency.When Mn concentration is 0.02 embodiment 206, can observe the raising of its luminosity, quantum yield.This reason is with above-mentioned identical.
When measuring the median size of embodiment 205 and 206, be 2.9 μ m with respect to the median size of embodiment 205, and the median size of embodiment 206 is 6.4 μ m.Difference according to this median size can be considered the reason that produces difference on luminosity.
Figure 27 A, B represent to take the photo of the particle diameter of fluor that does not add Mn and the fluor that adds Mn.Median size with respect to the fluor of the embodiment 205 that does not add Mn is 2.8 μ m, and the median size of fluor of adding the embodiment 206 of Mn is 6.4 μ m.The fluor of such interpolation Mn is compared to the fluorescence that does not add Mn, and then its particle diameter is bigger.The difference of this particle diameter can be considered the reason that can improve luminosity.
Embodiment 207 and 211.
The embodiment 207 of table 22 expression fluor of the present invention and 211 chemical property and physical property.
Table 22
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Sr/ To Mn mol alkali great soil group mole 1 mole of Eu mole- Tone x Tone y Brightness (%) Quantum yield Peak wavelength 100 ℃ 200 ℃
Si/Eu) + Eu mole=1 mole The alkali earths mole (％) (％) (％) (％)
207 10/0 1.94/5 /0.06 - 0.03 0.614 0.377 100.0 100.0 620 101.7 90.6
208 10/0 1.94/5 /0.06 0.005 0.03 0.616 0.375 102.6 106.0 621 101.5 83.8
209 10/0 1.94/5 /0.06 0.015 0.03 0.616 0.375 111.8 116.4 621 102 85.4
210 10/0 1.94/5 /0.06 0.05 0.03 0.618 0.373 105.6 114.9 626 102.7 86.8
211 10/0 1.94/5 /0.06 0.1 0.03 0.618 0.373 86.2 99.8 627 90.9 75.1
Embodiment 207 to 211 be the addition of the Mn of the fluor represented with Sr-Si-N:Eu of the present invention when changing chemical property or the result of study of the preferred property of thing.The raw material ratio of mixture of table 22 represents the raw material with mol ratio person.So and the fluor of making to be added with the general formula Sr of Mn (2-T)Eu TSi 5N 8Or contain the trace oxygen form and represent.Be not shown in embodiment 207 with adding Mn person.The addition of the Mn of the fluor use 0.01,0.03,0.1 and 0.2 of embodiment 208 to 211.Mn concentration during this situation is 0.005,0.015,0.05 and 0.1, and Mn concentration is the mol ratio to the volumetric molar concentration of Sr.The Eu concentration fixed is 0.03.
Embodiment 207 to 211 is because carry out the manufacturing process identical with embodiment 170 to 176, so omit locating of the identical formation of its experience.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
Fluor with the Mn that do not add embodiment 207 is that benchmark is represented luminous efficiency.Embodiment can observe the raising of luminosity at 208 to 210 o'clock.When particularly Mn concentration is 0.015 embodiment 209, can observe the raising of its luminosity.In addition, embodiment 208 to 210 quantum yielies are fabulous.And then the temperature profile of embodiment 208 to 211, even it is when changing the addition of Mn, also highly desirable.Peak wavelength then is offset to long wavelength side when increasing the addition of Mn.Though its reason is uncertain, Mn can be considered the reason of the diffusion of promotion raw material, particularly Eu.
Embodiment 212 to 220.
Chemical property and the physical property of the embodiment 212 to 220 of table 23 expression fluor of the present invention.
Table 23
Raw material The characteristics of luminescence Temperature profile
The Sr/Ca ratio Raw material ratio of mixture (Sr/Ca/ Si/Eu) To Mn mol alkali great soil group mole+Eu mole=1 mole 1 mole-alkali earths of Eu mole mole Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (%) 100 ℃ (％) 200 ℃ (％)
212 5/5 0.98/0.98 /5/0.04 - 0.02 0.624 0.366 100.0 100.0 638 101.7 92.5
213 5/5 0.98/0.98 /5/0.04 0.005 0.02 0.628 0.362 132.9 141.4 641 105.5 97.3
214 5/5 0.98/0.98 /5/0.04 0.015 0.02 0.628 0.362 144.5 151.5 641 101.8 85.4
215 5/5 0.98/0.98 /5/0.04 0.05 0.02 0.627 0.363 149.7 155.5 642 104.8 95.3
216 5/5 0.98/0.98 /5/0.04 0.1 0.02 0.623 0.367 128.9 129.6 641 105 95.3
217 5/5 0.98/0.98 /5/0.04 - 0.02 0.637 0.353 100.0 100.0 644 102.8 88.1
218 5/5 0.98/0.98 /5/0.04 0.02 0.02 0.638 0.353 105.1 105.7 644 101.1 86.5
219 7/3 1.386/0.5 94/5/0.02 - 0.01 0.620 0.371 100.0 100.0 627 102.1 93.4
220 7/3 1.386/0.5 0.01 0.01 0.622 0.370 105.8 105.1 628 102 94.2
94/5/0.02
Embodiment 212 to 220, chemical property or physical property when the addition of the Mn of the fluor of representing with Sr-Ca-Si-N:Eu of the present invention changes.The raw material ratio of mixture of table 23 represents the raw material with mol ratio person.So and the fluor of the embodiment 212 to 220 that makes, with general formula Sr XCa (2-X-T)Eu TSi 5N 8Or contain the trace oxygen form and represent.
Embodiment 212 to 220, because carry out the manufacturing process identical with embodiment 170 to 176, so omit locating of the identical formation of its experience.In this raw material, also can contain several ppm to Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni of hundreds of ppm more than at least a kind.
The Sr of embodiment 212 to 216 and the mol ratio of Ca are Sr: Ca=5: 5.Be not shown in embodiment 212 with what add Mn.The addition of the Mn of the fluor use 0.01,0.03,0.1 and 0.2 of embodiment 213 to 216.Mn concentration 0.005,0.015,0.05 and 0.1 during this situation, Mn concentration is the mol ratio to the volumetric molar concentration of Sr-Ca.The Eu concentration fixed is 0.02.
Fluor with the Mn that do not add embodiment 212 is that benchmark is represented luminous efficiency.Mn concentration is in 0.005,0.015,0.05 and 0.1 embodiment 213 to 216, and each all can observe the raising of its luminosity.In addition, also can be to reach the raising of quantum yield.And then temperature profile is also very preferred.Passing through like this is added on the represented fluor with Sr-Ca-Si-N:Eu with Mn, promptly can reach the raising of the characteristics of luminescence.
Embodiment 217 and 218 uses commercially available raw material and carries out the manufacturing of fluor of the present invention.Embodiment 217 and 218 Sr and the mol ratio Sr of Ca: Ca=5: 5.Be not shown in embodiment 217 with adding Mn person.The addition person of the Mn of the fluor use 0.04 of embodiment 218.The Mn concentration 0.02 of this situation, Mn concentration is to the mol ratio of the volumetric molar concentration of Sr-Ca.Eu concentration is 0.02.
Fluor with the Mn that do not add embodiment 217 is that benchmark is represented luminous efficiency.When making, also by adding the raising that Mn can reach the characteristics of luminescence using commercially available raw material.
Embodiment 219 and 220 uses commercially available raw material and carries out the manufacturing of fluor of the present invention.Embodiment 219 and 220 Sr and the mol ratio Sr of Ca: Ca=7: 3.Be not shown in embodiment 50 with adding Mn person.The addition of the Mn of the fluor use 0.02 of embodiment 220.Mn concentration during this situation is 0.01, and Mn concentration is the mol ratio to the volumetric molar concentration of Sr-Ca.Eu concentration is 0.01.
Fluor with the Mn that do not add embodiment 219 is that benchmark is represented luminous efficiency.Mn concentration is the raising that 0.01 embodiment 220 can reach the characteristics of luminescence.
Embodiment 217 and 218.
The result with the compositional analysis of the represented fluor of the Sr-Ca-Si-N:Eu of embodiments of the invention 217 and 218 is carried out in table 24 expression.
Table 24
Infer composition Sr (％) Ca (％) Ba (％) Si (％) Eu (％) Mn (ppm) O (％) N(％)
217 Sr 0.991Ca 0.983Ba 0.001Eu 0.039Si 5.00 0 O 0.309N 7.485 22.7 10.3 0.05 36.7 1.56 0 1.29 With full dose as 100% residual amount
218 Sr 0.991Ca 0.983Ba 0.001Eu 0.039Si 5.00 0 O 0.356N 7.457 22.7 10.3 0.05 36.6 1.54 8 1.49 With full dose as 100% residual amount
By above-mentioned analytical results can clear and definite above-mentioned fluor the having or not of Mn.In addition, in above-mentioned composition, contain 1～2% oxygen.
Embodiment 221.
The light-emitting device of embodiment 221 is the white color system light-emitting device of the Class1 of additional red composition, and Figure 28 is the figure of luminescent spectrum of the light-emitting device of expression embodiment 221, and Figure 29 is the figure that the expression color developing is estimated.
In the light-emitting device of embodiment 221, as fluor 11 and the fluor of mix embodiment 218 and YAG are fluor and using.Coating member 12 use with fixed ratio and blending epoxy and diffusant, barium titanate, titanium oxide and fluor 11.Modular unit 15 uses Resins, epoxy.The light-emitting device 1 of this bullet cut, the top of the radius 2～4mm of modular unit 15, high about 7～10mm is the round tube type of hemisphere.
When the light-emitting device of current flowing at this embodiment 221, the light that blue based light-emitting device 100 will have the 1st luminescent spectrum of peak wavelength 460nm carries out luminous, and make the fluor 11 that contains in covering the coating member 12 of this semiconductor layer 2 carry out wavelength conversion, and the light that will have 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum carries out luminous.In addition, the YAG that contains in fluor 11 is a fluor, and the light that will have the 3rd luminescent spectrum according to the light with the 1st luminescent spectrum carries out luminous.Have the colour mixture of the light of the 1st, the 2nd and the 3rd luminescent spectrum by mixing, and it is luminous to carry out reddish white color system.
The characteristics of luminescence of the characteristics of luminescence of the light-emitting device of table 25 expression present embodiment 221 and the light-emitting device of making in order to compare.Figure 28,29, table 25 also merge the measurement result of the light-emitting device of the light-emitting device of representing present embodiment 221 and comparative example.
As above-mentioned, the fluor 11 of the light-emitting device of present embodiment 221 is to use the fluor of mix embodiment 218 and the yttrium that is activated with cerium. gadolinium. and aluminum oxide is the fluor of fluor (Y-Gd-Al-O:Ce), but more specifically, uses (Y 0.8Gd 0.2) 3Al 5O 12: the fluor of Ce and as yttrium. gadolinium. aluminum oxide is fluorescent substance (Y-Gd-Al-O:Ce).
Excite this (Y with the light of Ex=460nm 0.8Gd 0.2) 3Al 5O 12: during the fluor of Ce, then be that the light of 562nm carries out luminous with peak wavelength.Similarly, the peak wavelength of the fluor of embodiment 218 is 650nm.
In embodiment 221, the weight ratio of fluor 11 and coating member is a coating member: the fluor of fluor (Y-Gd-Al-O:Ce): embodiment 218=10: 3.8: 0.6.On the other hand, the fluor of the light-emitting device of the combination of the blue based light-emitting device of comparative example and the fluor of Y-Gd-Al-O:Ce is with coating member: the weight ratio of fluor (Y-Gd-Al-O:Ce)=10: 3.6 and mixing.
The light-emitting device of embodiment 221 and the light-emitting device of comparative example are compared.The light-emitting device of embodiment 221 is compared to comparative example and tone no change almost, but color developing is improved.Learn that by Figure 29 it is inadequate that number R9 is estimated in the special colour developing of the light-emitting device of comparative example, but the R9 of the light-emitting device of embodiment 221 improves.In addition, relate to that other special colour developing estimates that number R is 8, R 10 etc. also improves the value that becomes more near 100%.And then in embodiment 221, lamp efficient is the higher numerical value of expression 24.91m/W.
Table 25
1. fluor
λp [nm] x y
Y-Gd-Al-O:Ce 562 0.457 0.527
Sr-Ca-Si-N:Eu 650 0.639 0.351
2. blend ratio
Blend ratio Coating member Y-Gd-Al-O:Ce Sr-Ca-Si-N:Eu
Comparative example (light-emitting device) 10 3.6 -
Embodiment 221 (light-emitting device) 10 3.8 0.6
3. measurement result
If [mA] Vf [V] Po [mV] Y [lm] λp Δλ λd x y Tcp [K] Ra Lamp efficient [lm/W]
Blueness-LED 20 3.7 14.1 0.66 456.9 19.5 461.2 0.145 0.037 - - 8.8
Comparative example (light-emitting device) 20 3.7 8.58 2.76 456.5 173.8 576.2 0.357 0.361 4599 76.2 37.0
Embodiment 221 (light-emitting device) 20 3.7 6.56 1.84 462.4 176.7 575.4 0.355 0.361 4671 87.7 24.9
Embodiment 222.
The light-emitting device of embodiment 222 is the light-emitting device of identical Class1, and is the light-emitting device of bulb look.Figure 30 is the figure that the color developing of the light-emitting device of expression present embodiment 222 is estimated.Figure 31 is the figure of luminescent spectrum of the light-emitting device of expression present embodiment 222.Figure 32 is the figure of tristimulus coordinates of the light-emitting device of expression present embodiment 222.The characteristics of luminescence of the light-emitting device of table 26 expression present embodiment 222.
In the light-emitting device 3 of present embodiment 222, fluor 11 is to use fluor that mixes example 218 and the yttrium that is activated with cerium. gallium. and aluminum oxide is the fluor of fluorescent substance (Y-Gd-Al-O:Ce).The light-emitting device 3 that also has embodiment 222 uses Y 3(Al 0.8Gd 0.2) 5O 12: the fluor of the composition of Ce and as yttrium. gallium. aluminum oxide is a fluorescent substance.
When this fluor excites with the light of Ex=460nm, then produce the light that peak wavelength is the luminescent spectrum of 533nm.Similarly, the peak wavelength of the fluor of embodiment 218 is 650nm.
This type of fluor 11 and coating member are with coating member: the weight ratio of the fluor of fluor (Y-Gd-Al-O:Ce): embodiment 218=10: 4.0: 1.08 and mixing.
Use and so to handle and the light-emitting device of the embodiment 222 of blended fluor, carry out the luminous of bulb look.During according to Figure 41 3 of tristimulus coordinates of the light-emitting device of expression embodiment 222, then tone X and tone Y are positioned at the luminous zone of white color system of warm colour system.The special colour developing of the light-emitting device of embodiment 222 is estimated number R9 and is also improved color developing 60%.The light-emitting device peak wavelength of embodiment 222 then is positioned at red area when being 620.7nm, and can obtain the white color system light-emitting device of bulb look.In the light-emitting device of embodiment 222, colour temperature position 2832K, color developing Ra position 90.4, and have the characteristics of luminescence near the bulb look.In addition, embodiment has the higher characteristics of luminescence of 19.21m/W.
Table 26
1. fluor
λp [nm] x y
Y-Gd-Al-O:Ce 533 0.383 0.575
Sr-Ca-Si-N:Eu 650 0.639 0.351
2. blend ratio
Blend ratio Coating member Y-Ga-Al-O:Ce Sr-Ca-Si-N:Eu
Embodiment 222 (light-emitting device) 10 4.0 1.08
3. measurement result
If [mA] Vf [V] Po [mV] Y [lm] λp Δλ λd x y Tcp [K] Ra Lamp efficient [lm/W]
Blueness-LED 20 3.7 14.1 0.66 456.9 19.5 461.2 0.145 0.037 - - 8.8
Embodiment 222 (light-emitting device) 20 3.7 5.3 1.42 620.7 238.1 583.6 0.449 0.407 2832 90.4 19.2
Embodiment 223.
The light-emitting device of embodiment 223 is the light-emitting device of type 3.
The light-emitting device of embodiment 223 use luminescence peak be have blue region 460nm InGaN based semiconductor layer luminous element 101 and as luminescent layer.
In addition, use fluor and the Y of embodiment 220 3(Al 0.8Gd 0.2) 5O 12: Ce and as fluor.
In the light-emitting device of the embodiment 223 that as above constitutes, blueness system with 1st luminescent spectrum luminous with luminous element 101, be the light that directly penetrate of light and self-emission device 101 with the indirect of baffle reflection for being radiated at fluor 108, and the luminous fluor of formation white color system.
In addition, by being light-emitting fluophor SrAl in fluor 108 doping greens of the present invention 2O 4: Eu, Y 2SiO 5: Ce, Tb, MgAl 11O 19: Ce, Tbg, Sr 7Al 12O 25: Eu, (Mg, Ca, Sr, Ba in more than at least 1) Ga 2S 4: Eu, blueness are light-emitting fluophor Sr 5(PO 4) 3Cl:Eu, (SrCaBa) 5(PO 4) 3Cl:Eu, (BaCa) 5(PO 4) 3Cl:Eu, (Mg, Ca, Sr, Ba in more than at least 1) 2B 5O 9Cl:Eu, Mn, (Mg, Ca, Sr, Ba in more than at least 1) (PO 4) 6Cl 2: Eu, Mn, red colour system light-emitting fluophor Y 2O 2S:Eu, La 2O 2S:Eu, Y 2O 3: Eu, Ga 2O 2The measure of S:Eu etc., the i.e. luminescent spectrum that can obtain to expect.
Use as above and the light-emitting device that forms and when making white led lamps, can obtain 99% yield rate.So,, can productivity produce well, and can provide reliability the higher and less light-emitting device of phenomenon mottle according to present embodiment 222.
＜relate to the embodiment 224～245 of embodiment 5 〉
The characteristics of luminescence of the fluor of embodiment 224～243 is to make 100% relative brightness with the brightness of comparative example 2 and to represent.
Embodiment 224～229.
The embodiment 224～229 and the comparative example 2～3 of table 27 expression nitride phosphor of the present invention.In addition, Figure 34 to 36 represents the characteristics of luminescence of the nitride phosphor of embodiment 225 and 226.Figure 34 is the figure of the luminescent spectrum of expression when exciting the nitride phosphor of embodiment 225 and 226 with Ex=460nm.Figure 35 is the figure of the excitation spectrum of expression embodiment 225 and 226 nitride phosphor.Figure 36 is the accompanying drawing of the reflection spectrum of expression embodiment 225 and 226 nitride phosphor.Figure 37 is the photo of particle diameter of taking the nitride phosphor of embodiment 226.
Table 27 (1)
Raw material The result
The basic comprising element Raw material ratio of mixture (Ca/Si/Eu) Other elements Burn till pattern Crucible material Atmosphere Medium particle diameter (Dm/ σ log) Medium particle diameter () (Dm/ σ log)
Embodiment 224 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 - 1 stage, 1350 ℃ * 5h BN NH 3 5.33/0.410 4.69/0.378
Embodiment 225 Ca 1.99Si 5N 8:Eu 0.01 1.99/5/0.01 - 1 stage, 1350 ℃ * 5h BN NH3 5.61/0.412 4.31/0.415
Embodiment 226 Ca 1.94Si 5N 8:Eu 0.06 1.94/5/0.06 - 1 stage, 1350 ℃ * 5h BN NH 3 5.13/0.366 4.67/0.419
Embodiment 227 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 - 2 stages, 800 ℃ * 3h, 1350 ℃ * 5h BN NH 3 - -
Embodiment 228 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 B 1 stage, 1350 ℃ * 5h BN NH 3 - -
Embodiment 229 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 Al 1 stage, 1350 ℃ * 5h Al 2O 3 NH 3 - -
Comparative example 2 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 - 1 stage, 1350 ℃ * 5h Mo NH 3 - -
Comparative example 3 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 Fe 1 stage, 1350 ℃ * 5h BN NH 3 - -
Table 27 (2)
The characteristics of luminescence (460nm) Temperature profile (%)
Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (nm) 100℃ 200℃ 300℃
Embodiment 224 0.583 0.406 135.5 139.0 612 93.7 67.1 23.5
Embodiment 225 0.583 0.410 97.6 96.5 610 99.8 81.1 37.1
Embodiment 226 0.590 0.401 139.4 148.0 614 92.9 56.1 12.5
Embodiment 227 0.584 0.400 128.7 136.8 612 97.7 70.6 22.6
Embodiment 228 0.587 0.405 137.6 141.1 612 95.8 65.8 21.6
Embodiment 229 0.586 0.406 116.1 119.1 611 95.7 68.1 22.6
Comparative example 2 0.581 0.410 100.0 100.0 610 97.9 72.7 25.7
Comparative example 3 0.58 0.411 65.1 65.4 611 99.6 79.6 29.6
Table 27 (3)
Ca(％) Eu(％) N(％) O(％) Fe (ppm) Mg (ppm) Sr (ppm) Ba (ppm) Zn (ppm) B (ppm) Al (ppm) Mo (ppm) Mn (ppm) Cu (ppm) Si
Embodiment 224 23.1 1.22 29.4 0.87 7 7 180 1 9 ＜1 110 ＜1 ＜1 ＜1 Total amount is 100% residual amount
Embodiment 225 23.7 0.46 31.3 1.35 6 13 70 6 360 ＜1 30 ＜1 1 ＜1 Total amount is 100% residual amount
Embodiment 226 22.4 2.40 31.5 0.97 8 15 50 6 5 ＜1 30 ＜1 1 1 Total amount is 100% residual amount
Embodiment 227 23.2 1.20 29.3 0.80 7 8 150 5 5 ＜1 90 ＜1 1 ＜1 Total amount is 100% residual amount
Embodiment 228 23.1 1.21 29.3 0.90 9 7 110 6 7 510 100 ＜1 ＜1 ＜1 Total amount is 100% residual amount
Embodiment 229 23.0 1.21 29.3 0.95 9 10 120 6 4 ＜1 90 ＜1 1 ＜1 Total amount is 100% residual amount
Comparative example 2 23.1 1.22 29.4 0.85 9 8 120 5 4 ＜1 30 490 1 1 Total amount is 100% residual amount
Comparative example 3 23.1 1.22 29.3 0.98 480 8 140 6 5 ＜1 90 ＜1 1 1 Total amount is 100% residual amount
Embodiment 224～229th, at L of the present invention XM YN (2/3X+4/3Y): contain among the R be selected from, the chemical property of the nitride phosphor more than at least a kind among B, Al, Cu, Mn, Co, Ni, Mo, O and the Fe or the result of study of physical property.Nitride phosphor L XM YN (2/3X+4/3Y): the L of the substrate nitride phosphor of R system uses Ca, and M uses Si, and R system uses Eu, and with Ca 2-tEu tSi 5N 8Expression.Replace the part of use with Eu, and represent the cooperation ratio of Eu, represent the cooperation ratio of Ca with 2-t with t at the Ca of the nitride phosphor of embodiment 224～229.With respect to 5 of Si, then embodiment 224 contains with 0.03, and embodiment 225 contains with 0.01, and embodiment 226 contains the Eu with 0.06 represented cooperation ratio.
To contain several ppm CaCl2, silicon nitride, europium sesquioxide more than at least a kind to Mg, Sr, Ba, Zn, B, Al, Cu, Mn and the Fe of hundreds of ppm mixes.In embodiment 224, the CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Mixture ratio (mol ratio), can form Sr: Si: Eu=1.97: 5: 0.03.
CaCl2 Ca 3N 214.47g
Silicon nitride Si 3N 434.75g
Europium sesquioxide Eu 2O 30.79g
The mixing above-claimed cpd also burns till.Firing condition is in ammonia atmosphere, is fed into boron nitride crucible, through about 5 hours and heat up lentamente from room temperature, and carries out 5 hours burn till with about 1350 ℃, and is cooled to room temperature lentamente through 5 hours.
According to table 27, the nitride phosphor of embodiment 224 is except the substrate nitride phosphor, and containing O is 0.87 weight %, contains Mg, Sr, Ba, Zn, B, Al, Cu, Mn and Fe then and is number ppm.Si contains and is selected from 100 and cut the weight % of above-mentioned formation element.Has higher luminosity by this firing condition and Mg, Sr, Ba, Zn, B, Al, Cu and Mn.Because ascending temperature to 100～150 of general employed semiconductor light-emitting elements ℃, so form nitride phosphor when luminous element surperficial, reach stable with this temperature and serve as preferred, the temperature profile of the nitride phosphor of present embodiment 224 to 229 is very preferred.From this viewpoint, embodiment 225 is because its temperature profile is fabulous, so have the meaning of excellent technical elements.
When embodiment 226 and embodiment 225 compared, its luminosity was higher, and quantum yield is also high.Therefore, embodiment 226 shows the fabulous characteristics of luminescence.
During particle diameter position 1～3 μ m of embodiment 224, then particle diameter is big and luminosity is also higher.In addition, dispersed might as well and be easy to handle.
Embodiment 227 changes firing condition and carries out burning till of raw material.Even be to burn till in 2 stages, and embodiment 227 is also identical with 226 with embodiment 224, exhibit high brilliance, high-quantum efficiency, fabulous temperature profile.
The fluor of embodiment uses the crucible of boron nitride material, burns till in ammonia atmosphere.Under this firing condition, because the situation of no etch stove and crucible is sneaked into to the phenomenon of burning till product so nothing is sneaked into impurity.Embodiment 228 expression contains B in raw material and luminous efficiency when burning till.According to the result of embodiment 228, even when then containing more B, its luminous efficiency also can be to maintain high state.Though this situation hypothesis contains BN in the fluor of etch stove material and BN crucible, because its luminous efficiency does not have decline, so the etch of stove material and crucible promptly is out of question, can burn till.Also promptly, suppose the result that under this condition, burns till, even it is when containing the boron nitride of etch in fluor, also unlikely reducing luminosity, so extremely useful.
Embodiment 229 expressions contain the characteristics of luminescence of the fluor of most aluminium.Except the crucible of BN, when also considering to use alumina crucible because of etch phenomenon that alumina crucible caused.According to the result of embodiment 229, even also show the higher characteristics of luminescence for the fluor that contains aluminium.Even when using the situation of alumina crucible therefrom, do not have the pollution problem that causes because of alumina crucible yet, and can burn till.
With respect to this, comparative example 2 uses molybdenum crucible.When using molybdenum crucible, the molybdenum of etch crucible contains in fluor.The fluor that contains the comparative example 2 of molybdenum produces the phenomenon that the characteristics of luminescence descends.Therefore, use molybdenum crucible preferred not to the utmost.Because Mo descends the characteristics of luminescence, so remove to preferred.
Comparative example 3 is made Fe is contained in fluor.Because according to the pollution that causes because of molybdenum crucible and stove material, and also there is Fe to contain situation in fluor, so measure the effect when containing Fe in fluor.Its result is because Fe also makes the characteristics of luminescence descend, so remove to preferred.
Comparison test.
For clear and definite action effect of the present invention, and then compare test.Comparative example 4 is with respect to the nitride phosphor that only contains the substrate nitride phosphor, and embodiment 224 and 227 then contains the nitride phosphor of substrate nitride phosphor and composition formation element.This result is shown in table 28.Figure 38 is the luminescent spectrum graphic representation of expression when exciting the nitride phosphor of embodiment 224 and comparative example 4 with Ex=460nm.
Make the CaCl2 Ca of the raw material of comparative example 4 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3The cooperation ratio, be adjusted to Ca: Si: Eu=1.97: 5: 0.03, and use and can fully carry out the refiner and make raw material.On the other hand, the cooperation ratio of the raw material of embodiment 227 uses and comparative example 4 the same terms persons, and contains several ppm and Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, Mn and Fe the embodiment same concentrations in this raw material.3 raw materials of compound that embodiment 227 will contain Mn etc. are fed into the BN crucible, heat up lentamente from room temperature, and approximately carry out burning till in 3 hours with 800 ℃, and then heat up lentamente, approximately carry out burning till in 5 hours with 1350 ℃, and after burning till, be cooled to room temperature lentamente through 5 hours.3 raw materials of compound that comparative example 4 will not contain Mn etc. are fed into molybdenum crucible, and burn till in hydrogen/nitrogen atmosphere.As 1 o'clock, then the flow of the hydrogen/nitrogen of comparative example 4 was a hydrogen with the flow of the ammonia of embodiment 227: the ratio of nitrogen=0.1: 3.On the other hand, embodiment 224 heats up in ammonia atmosphere lentamente, and carries out burning till in 5 hours with about 1350 ℃, and is cooled to room temperature lentamente through 5 hours.
Table 28 (1)
Raw material
The basic comprising element Raw material ratio of mixture (Ca/Si/Eu) Ca 3N 2 Si 3N 4 Eu 2O 3 Burn till pattern The crucible material Atmosphere Gas flow
Comparative example 4 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 2.89 6.95 0.16 800 ℃ * 3 hours 1350 ℃ * 5 hours 2 stages BN H 2/N 2
Embodiment 227 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 14.47 34.75 0.79 800 ℃ * 3 hours 1350 ℃ * 5 hours 2 stages BN NH 3
Embodiment 24 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 14.47 34.75 0.79 1350 ℃ * 5 hours 1 stage BN NH 3
Table 28 (2)
The characteristics of luminescence Temperature profile
Tone X Tone Y Brightness (%) Quantum yield (%) Energy (%) 100℃ 200℃ 300℃
Comparative example 4 0.585 0.407 99.1 100.5 99.1 93.3 62.8 18.2
Embodiment 227 0.584 0.406 128.7 136.8 131.1 97.7 70.6 22.6
Embodiment 24 0.585 0.406 135.5 138.6 138.0 93.7 67.1 23.5
Make the CaCl2 Ca of the raw material of comparative example 4 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3The cooperation ratio, be adjusted to Ca: Si: Eu=1.97: 5: 0.03, and use and can fully carry out the refiner and make raw material.On the other hand, the cooperation ratio of the raw material of embodiment 227 uses and comparative example 4 the same terms persons, and contains several ppm and Mg, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr, Mn and Fe the embodiment same concentrations in this raw material.3 raw materials of compound that embodiment 227 will contain Mn etc. are fed into the BN crucible, heat up lentamente from room temperature, and approximately carry out burning till in 3 hours with 800 ℃, and then heat up lentamente, approximately carry out burning till in 5 hours with 1350 ℃, and after burning till, be cooled to room temperature lentamente through 5 hours.3 raw materials of compound that comparative example 4 will not contain Mn etc. are fed into molybdenum crucible, and burn till in hydrogen/nitrogen atmosphere.As 1 o'clock, then the flow of the hydrogen/nitrogen of comparative example 4 was a hydrogen with the flow of the ammonia of embodiment 227: the ratio of nitrogen=0.1: 3.On the other hand, embodiment 224 heats up in ammonia atmosphere lentamente, and carries out burning till in 5 hours with about 1350 ℃, and is cooled to room temperature lentamente through 5 hours.
Learnt that by table 28 and Figure 38 the luminosity of comparative example 4 is with respect to 99.1%, during the luminosity 128.7% of embodiment 227, its luminosity improves 29.6%.The viewpoint of luminous efficient, the difference of this luminosity has epochmaking meaning.To the energy efficiency 99.1% at comparative example 4, and the energy efficiency of embodiment 227 is 131.1%, and this also improves 32%.And then be 100.5% to the quantum yield at comparative example 4, and the quantum yield of embodiment 227 is 136.8%, this also improves 36.3%.So, by changing the material of atmosphere and crucible, can obtain the very significantly characteristics of luminescence.In addition, by containing the measure of Mg, Mn etc., can obtain the very significantly characteristics of luminescence.So the raising of the characteristics of luminescence of handling can provide the distincter luminous luminescent material of white color system.In addition, because the raising of the characteristics of luminescence can improve energy efficiency, so also can be to reach province's electrification.
And then embodiment 224 is compared to embodiment 227, except the difference of the pattern of burning till, burns till with identical condition.The pattern of burning till of embodiment 224 heats up lentamente from room temperature, approximately carries out burning till in 5 hours with 1350 ℃.Be cooled to room temperature lentamente through 5 hours.The luminous energy efficient of this moment is 134.3%, is compared to comparative example 4 and also improves 34.6%.In addition, energy efficiency is 136.8%, is compared to comparative example 4 and also improves 36.8%.And then quantum yield is 139.3%, is compared to comparative example 4 and also improves 39.3%.And then change and when observing its temperature profile with the relative brightness of organizing in determined group as 100 with room temperature, to being 62.8% o'clock for 200 ℃ in comparative example 4 temperature, and embodiment 224 is 67.1% at uniform temp, then shows higher numerical value.In addition, 300 ℃ with respect to 18.2% of comparative example 4, the 23.5% higher numerical value of demonstration then of embodiment 224.This temperature profile makes and this nitride phosphor is set when luminous element surperficial, and the composition of nitride phosphor does not change, and expression shows the higher characteristics of luminescence.The temperature profile height of healing is then represented more stable.Result according to table 28 can confirm that nitride phosphor of the present invention is compared to comparative example 4 and its temperature profile is better, and reliability is higher.So embodiment 224 and 227 is compared to comparative example 4 and shows the very significantly characteristics of luminescence.Thus promptly can the utmost point reach the raising of the not soluble characteristics of luminescence in the past easily.
Embodiment 230～232.
Embodiment 230 is that the substrate nitride phosphor is Sr 1.97Eu 0.03Si 5N 8The cooperation ratio of raw material is CaCl2 Sr 3N 2: silicon nitride Si 3N 4: europium sesquioxide Eu 2O 3=1.97: 5: 0.03.Mg, the Ca, Sr, Ba, Zn, B, Al, Cu, Mn, Co and the Fe that in this raw material, contain 250～400ppm concentration.This 3 raw materials of compound is fed in the BN crucible, burnt till 3 hours with 800～1000 ℃, after this, carry out burning till in 5 hours, be cooled to room temperature through 5 hours lentamente with 1250～1350 ℃ at tube furnace.Ammonia continues circulation all the time with the ratio of 11/min.Its result, the temperature profile that the nitride phosphor of embodiment 230 is 200 ℃ 87.7% show high temperature profile.The embodiment 230～232 of table 29 expression nitride phosphor of the present invention.
Table 29 (1)
Raw material
The basic comprising element The raw material ratio of mixture Burn till pattern Atmosphere Crucible material Raw material (g)
Embodiment 230 Sr 1.97Si 5N 8:Eu 0.03 Sr/Si/Eu＝1.07/5/0.03 2 stages, 800～1000 ℃ * 3h, 1250～1350 ℃ * 5h NH 3 BN 4.47
Embodiment 231 Sr 1.4Ca 06Si 5N 8:Eu Sr/Ca/Si/Eu＝1.26/0.54/5/0.2 2 stages, 800～1000 ℃ * 3h, 1250～1350 ℃ * 5h NH 3 BN 8.8
Embodiment 232 Sr 1.4Ca 0.6Si 5N 8:Eu Sr/Ca/Si/Eu＝1.379/0.591/5/0.03 2 stages, 800～1000 ℃ * 3h, 1250～1350 ℃ * 5h NH 3 BN 8.8
Table 29 (2)
The characteristics of luminescence (460nm) Temperature profile (%)
Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (nm) 200℃
Embodiment 230 0.612 0.379 96.5 110.2 621 87.7
Embodiment 231 0.649 0.341 58.8 151.9 657 92.3
Embodiment 232 0.655 0.366 89.9 1193.5 637 97.9
Among the embodiment 231, substrate nitride phosphor Sr 1.4Ca 0.6Si 5N 8: Eu.In the raw material of this fluor, strontium nitride, CaCl2, silicon nitride, metal europium, approximately contain Mg, Sr, Ba, Zn, B, Al, Cu, Mn, Co and the Fe of 250～350ppm concentration.Embodiment 231 is to burn till with embodiment 230 identical firing conditions.Figure 39 is the figure of the luminescent spectrum of expression when exciting embodiment 231 with Ex=460nm.Learn that by Figure 39 when the light time of the luminescent spectrum that shines Ex=460nm, when being compared to the Sr of independent use II valency, then combination S r and Ca hour offset are to long wavelength side.The peak value 657nm of luminescent spectrum.During the fluor of combined blue based light-emitting device and embodiment 231, promptly can obtain the luminous fluor of reddish white color system therefrom.In addition, the fluor Sr of embodiment 231 1.4Ca 0.6Si 5N 8: the quantum yield of Eu is 151.9% and highly desirable.
Embodiment 232 is the cooperation ratios that change Eu.Embodiment 232 is also identical with other embodiment, shows the fabulous characteristics of luminescence.In addition, make emission wavelength form 637nm by changing Eu concentration.Temperature profile is then to show higher numerical value at 97.9% o'clock with 200 ℃, so the expression high stability.
Embodiment 233 to 243.
Embodiment 233 to 243 carries out the mensuration of twilight sunset.Table 30 is measured the result of the twilight sunset of embodiment 233 to 243.Figure 40 represents to measure the measurement result of the twilight sunset of embodiment 233.
Table 30
The basic comprising element Compound Addition (wt%) 1/10 twilight sunset (msec)
No additive Ca 1.94Si 5N 8:Eu 0.06 - - 20.5
Embodiment 233 Ca 1.94Si 5N 8:Eu 0.06 BN 0.25 6.5
Embodiment 234 Ca 1.94Si 5N 8:Eu 0.06 BN 0.75 14.5
Embodiment 235 Ca 1.94Si 5N 8:Eu 0.06 BN 1.50 16.5
Embodiment 236 Ca 1.94Si 5N 8:Eu 0.06 BN 3.00 18.0
Embodiment 237 Ca 1.94Si 5N 8:Eu 0.06 H 3BO 3 0.25 10.5
Embodiment 238 Ca 1.94Si 5N 8:Eu 0.06 H 3BO 3 0.75 9.5
Embodiment 239 Ca 1.94Si 5N 8:Eu 0.06 H 3BO 3 1.50 13.0
Embodiment 240 Ca 1.94Si 5N 8:Eu 0.06 H 3BO 3 3.00 16.5
Embodiment 241 Ca 1.94Si 5N 8:Eu 0.06 Mg 3N 2 0.05 7.0
Embodiment 242 Ca 1.94Si 5N 8:Eu 0.06 Mg 3N 2 0.10 11.0
Embodiment 243 Ca 1.94Si 5N 8:Eu 0.06 Mg 3N 2 0.20 14.5
The mensuration of embodiment 233 to 243 is the ultraviolet ray of irradiation 254nm, and will stop to shine just after luminous intensity make 1.Measure oneself and just stopped shining the back time till luminous intensity formation 1/10.Table 30 be luminous intensity be form 1/10 till the needed time.Embodiment 233 to 243 removes the fluor of embodiment 224 and additive and is same composition.Also promptly, substrate nitride phosphor Ca 1.97Eu 0.03Si 5N 8, composition constitutes element M g, Ca, Sr, Ba, Zn, B, Al, Cu, Mn, Co and Fe, and composition formation element contains 250～400ppm concentration.The BN, the H that contain several weight % concentration 3BO 3, Mg 3N 2In the raw material of this embodiment 224.The raw material that will contain B and Mg is fed in the BN crucible and burns till.Embodiment 233 to 236 is with BN, and embodiment 237 to 240 is with H 3BO 3, embodiment 241 to 243 is with Mg 3N 2Use level that use is decided.Contrast and the fluor that will not contain additive uses in benchmark value as a comparison.Its result, twilight sunset are that the middle embodiment 233 of embodiment 233 to 236 is for the shortest.Embodiment 237 is for the shortest among the embodiment 237 to 240, and embodiment 241 is for the shortest among the embodiment 241 to 243.So, by adding quantitative B, Mg, promptly can suppress persistence characteristic.
Other embodiment.
The various embodiment of expression nitride phosphor.Nitride phosphor of the present invention is at L XM YN (2/3X+4/3Y): the substrate nitride phosphor of R, contain the nitride phosphor more than a kind that is selected from the group that Mg, Sr, Ba, Zn, B, Al, Cu, Mn, Co, Ni, Mo, O and Fe form.The L of this substrate nitride phosphor contain in the group that the II valency that is selected from Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg formed more than at least a kind, M contain in the group that the IV valency that is selected from C, Si, Ge, Sn formed more than at least a kind, R is an activator.Activator R, Eu is preferred, but also can use Cr, Mn, Pb, Sb, Ce, Tb, Sm, Pr, Tm, Ho, Er etc.
The substrate nitride phosphor can be made Sr 2Si 5N 8: Eu, Ba 2Si 5N 8: Eu, Mg 2Si 5N 8: Eu, Zn 2Si 5N 8: Eu, SrSi 7N 10: Eu, BaSi 7N 10: Eu, MgSi 7N 10: Eu, ZnSi 7N 10: Eu, Sr 2Ge 5N 8: Eu, Ba 2Ge 5N 8: Eu, Mg 2Ge 5N 8: Eu, Zn 2Ge 5N 8: Eu, Sr 2Ge 7N 10: Eu, BaGe 7N 10: Eu, MgGe 7N 10: Eu, ZnGe 7N 10: Eu, Sr 1.8Ca 0.2Si 5N 8: Eu, Ba 1.8Ca 0.2Si 5N 8: Eu, Mg 1.8Ca 0.2Si 5N 8: Eu, Zn 1.8Ca 0.2Si 5N 8: Eu, Sr 0.8Ca 0.2Si 7N 10: Eu, Ba 0.8Ca 0.2Si 7N 10: Eu, Mg 0.8Ca 0.2Si 7N 10: Eu, Zn 0.8Ca 0.2Si 7N 10: Eu, Sr 0.8Ca 0.2Ge 7N 10: Eu, Ba 0.8Ca 0.2Ge 7N 10: Eu, Mg 0.8Ca 0.2Ge 7N 10: Eu, Zn 0.8Ca 0.2Ge 7N 10: Eu, Sr 0.8Ca 0.2Si 6GeN 10: Eu, Ba 0.8Ca 0.2Si 6GeN 10: Eu, Mg 0.8Ca 0.2Si 6GeN 10: Eu, Zn 0.8Ca 0.2Si 6GeN 10: Eu, Sr 2Si 5N 8: Pr, Ba 2Si 5N 8: Pr, Sr 2Si 5N 8: Tb, BaGe 7N 10: Ce etc.
But the invention is not restricted to this nitride phosphor.
Embodiment 244.
The light-emitting device of embodiment 244 is the light-emitting device of type 2.
Use luminescence peak be have blue region 460nm the InGaN semiconductor layer semiconductor light-emitting elements 101 and as luminescent layer.This semiconductor light-emitting elements 101 is formed with p type semiconductor layer and n type semiconductor layer (not shown).This p type semiconductor layer and n type semiconductor layer are formed with conducting wire 104, and it is linked to lead-in wire electrode 102.Be formed with insulated enclosure material 103 with the state of the periphery that can cover lead-in wire electrode 102, and prevent short circuit phenomenon.The window portion 107 of light transmission is set above semiconductor light-emitting elements 101, and it is from the lead-in wire 106 on the top of encapsulation 105 and extend.Inner face in the window portion 107 of this light transmission is the homogeneous mixture that roughly is coated with nitride phosphor 108 of the present invention and coating member 109 all sidedly.Light-emitting device 1 is to use the nitride phosphor of embodiment 223.Encapsulation 105 is that one side of removing the bight is the square of 8mm～12mm.
Carrying out blueness with semiconductor light-emitting elements 101 is luminous luminescent spectrum, be the indirect luminescent spectrum that reflects with reflector and from semiconductor light-emitting elements 101 and the luminescent spectrum that directly penetrates for being radiated at nitride phosphor 108 of the present invention, and the luminous fluor of formation white color system.By being doped with green at nitride phosphor 108 of the present invention is light-emitting fluophor SrAl 2O 4: Eu, Y 2SiO 5: Ce, Tb, MgAl 11O 19: Ce, Tb, Sr 7Al 12O 25: Eu, (Mg, Ca, Sr, Ba in more than at least 1) Ga 2S 4: Eu, blueness are light-emitting fluophor Sr 5(PO 4) 3Cl:Eu, (SrCaBa) 5(PO 4) 3Cl:Eu, (BaCa) 5(PO 4) 3Cl:Eu, (Mg, Ca, Sr, Ba in more than at least 1) 2B 5O 9Cl:Eu, Mn, (Mg, Ca, Sr, Ba in more than at least 1) (PO 4) 6Cl 2: Eu, Mn, red colour system light-emitting fluophor Y 2O 2S:Eu, La 2O 2S:Eu, Y 2O 3: Eu, Ga 2O 2S:Eu etc., the i.e. luminescent spectrum that can obtain to expect.
The light-emitting device that uses processing as above and form and when forming the White LED electric light, promptly yield rate 99%.So, the photodiode of the application of the invention promptly can produce the fabulous light-emitting device of productivity, and can provide reliability the higher and less light-emitting device of phenomenon mottle.
Embodiment 245.
The light-emitting device of embodiment 245 is the light-emitting device of Class1.Figure 41 4 is figure of luminescent spectrum of the light-emitting device of expression present embodiment 245.Figure 42 is the figure of tristimulus coordinates of the light-emitting device of expression present embodiment 245.
Light-emitting device is formed with the semiconductor layer 2 of the GaN layer of n type and p type on sapphire substrate 1, and on the semiconductor layer 2 of this n type and p type electrode 3 is set, and this electrode 3 is electrically connected with lead frame 13 by conducting wire 14.The top of semiconductor light emitting element 10 covers with fluor 11 and coating member 12, and covers the periphery of lead frame 13, fluor 11 and coating member 12 etc. with modular unit 15.Semiconductor layer 2 has stacked gradually n on sapphire substrate 1 +GaN:Si, n-Al GaN:Si, n-GaN, GaInNQWs, P-GaN:Mg, P-AlGaN:Mg, P-GaN:Mg.This n +The part of GaN:Si layer is formed with n type electrode through etching.On this P-GaN:Mg layer, be formed with p type electrode.Lead frame 13 uses ferruginous copper.The top that lead-in wire 13a is installed is provided with cup, and for use in loading semiconductor light-emitting elements 10, and this semiconductor light-emitting elements 10 is bonded on the bottom surface of the substantial middle portion of this glass.Conducting wire 14 uses gold, imposes plating Ni in order to the projection 4 of conduction connection electrode 3 and conducting wire 14.Fluor 11 is that fluor mixes with nitride phosphor and the YAG of embodiment 224.The material that coating member 12 uses with institute's certainty ratio blending epoxy and diffusant, barium titanate, titanium oxide and above-mentioned fluor 11.Model assembly 15 uses Resins, epoxy.The light-emitting device 2 of this bullet cut is the radius 2～4mm of modular unit 15, and the top of highly about 7～10mm is the round tube type of hemisphere.
Circulating current is when light-emitting device 2, then have blue semiconductor luminous element 10 exciting lights of exciting light the 1st luminescent spectrum with about 460nm, the nitride phosphor 11 that the 1st luminescent spectrum is covered semiconductor layer 2 carries out tone reversal, and has 2nd luminescent spectrum different with above-mentioned the 1st luminescent spectrum.In addition, the YAG that contains in fluor 11 is a fluor, shows the 3rd luminescent spectrum by the 1st luminescent spectrum.1st, the mutual colour mixture of the 2nd and the 3rd luminescent spectrum can provide the luminous light-emitting device of reddish white color system 2.
Figure 42 also together expression to use YAG be the measurement result of the light-emitting device of fluor, and as the comparison other of the light-emitting device 2 of present embodiment 245.
The nitride phosphor of the light-emitting device of present embodiment 245, use nitride phosphor, the coating member 12 of mix embodiment 224 and the YAG that is activated with cerium (yttrium. aluminium. garnet) fluor 11 of fluorescent substance.The weight ratio of this type of fluor 11 is the nitride phosphor=25: 6: 3 of coating member: YAG: embodiment 224.On the other hand, blue semiconductor luminous element and YAG are the fluor of light-emitting device of the combination of fluor, with coating member: YAG=25: 6 weight ratio and mixing.
With the light-emitting device of present embodiment 245 with to use blue semiconductor luminous element and YAG be that the light-emitting device of fluor compares.To the fluor peak wavelength at this YAG is 463.47NM, and then the peak wavelength of nitride phosphor has luminescent spectrum in the position different with 596.00nm.In tristimulus coordinates, only use the light-emitting device of the fluor of YAG, be with tone x=0.348, the white of the comparatively blue white hair light that tone y=0.367 is represented.On the other hand, using YAG is the light-emitting device 2 of fluor and nitride phosphor, with tone x=0.454, and the reddish white that tone y=0.416 is represented.Colour temperature is 2827.96K, and color developing Ra is 76, and has the characteristics of luminescence near the bulb look.In addition, light-emitting device 2 of the present invention has the high-luminous-efficiency of 24.871m/W.
Thus, has the very important techniques meaning that to make near the light-emitting device of bulb look.
＜relate to the embodiment 246～256 of embodiment 6 〉
Embodiment 246～255.
Comparison test.
For clear and definite effect of the present invention, except the difference of atmosphere, be to burn till with identical condition.Its result is shown in table 32.Figure 44 is the figure of the luminescent spectrum of expression when exciting embodiment 247 and comparative example 10 with Ex=460nm.
Table 32 (1)
Raw material The result
The basic comprising element Raw material ratio of mixture (Ca/Si/Eu) Ca 3N 2 Si 3N 4 Eu 2O 3 Burn till pattern Atmosphere () flow The bodyguard amount The receipts amount Body colour Visual luminous (365nm)
Comparative example 10 Ca 2Si 5N 8:Eu 1.97/5/0.03 2.89 6.95 0.16 2 stages, 800 ℃ * 3h, 1350 ℃ * 5h H 2/N 2 0.1/3 10.00 9.05 Orange Orange
Embodiment 246 Ca 2Si 5N 8:Eu 1.97/5/0.03 14.47 34.75 0.79 2 stages, 800 ℃ * 3h, 1350 ℃ * 5h NH 3 1 50.01 49.10 Orange Orange
Embodiment 247 Ca 2Si 5N 8:Eu 1.97/5/0.03 14.47 34.75 0.79 1 stage, 1350 ℃ * 5h NH 3 1 50.01 49.10 Orange Orange
Table 32 (2)
The characteristics of luminescence (460nm) Temperature profile
Tone x Tone y Brightness (%) Energy efficiency (%) Quantum yield (%) 100℃ (％) 200℃ (％) 300℃ (％)
Comparative example 10 0.598 0.401 59.9 57.1 57.3 93.3 62.8 18.2
Embodiment 246 0.597 0.400 77.9 74.7 78.0 97.7 70.6 22.6
Embodiment 247 0.598 0.400 82.0 78.8 79.1 93.7 67.1 23.5
Embodiment 246 and comparative example 10, the CaCl2 Ca of its raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3The cooperation ratio, be adjusted to Ca: Si: Eu=1.97: 5: 0.03.This 3 raw materials of compound is fed into the BN crucible, heats up lentamente from room temperature, and approximately carry out burning till in 3 hours with 800 ℃, and then heat up lentamente, approximately carrying out burning till in 5 hours, and after burning till, be cooled to room temperature lentamente through 5 hours with 1350 ℃.Comparative example 10 burns till in hydrogen/nitrogen atmosphere.The flow of the ammonia of embodiment 246 was made the flow of the hydrogen/nitrogen of comparative example 10 then, hydrogen: the ratio of nitrogen=0.1: 3 at 1 o'clock.On the other hand, embodiment 246 burns till in ammonia atmosphere.
By table 32 and Figure 44 and learn that with respect to the luminosity 100 of comparative example 10, and the luminosity of embodiment 246 is 130%, also improve 30% luminosity.The viewpoint of luminous efficient, the difference of this luminosity has very important meaning.The energy efficiency of comparative example 10 was made 100% o'clock, and then the energy efficiency of embodiment 246 is 130.8%, also improves 30.8%.And then the quantum yield of comparative example 10 is with respect to 100%, and the quantum yield of embodiment 246 is 136.1%, also improves 36.1%.So, by changing atmosphere, promptly can obtain the very significant characteristics of luminescence.The raising of such characteristics of luminescence can provide the distincter luminous luminescent material of white color system.In addition, the raising of the characteristics of luminescence also can be to reach province's electrification because can improve energy efficiency.
And then embodiment 247 is compared to embodiment 246 and outside the difference of the pattern of burning till, burns till with identical condition.The pattern of burning till of embodiment 247 is to heat up lentamente from room temperature, carries out burning till in 5 hours with about 1350 ℃, and is cooled to room temperature through 5 hours lentamente.The luminosity of this moment is 136.9%, is compared to comparative example 10 and also improves 36.9%.In addition, energy efficiency is 138%, is compared to comparative example 10 and also improves 38%.And then quantum yield 138%, be compared to comparative example 10 and also improve 38%.And then room temperature made 100%, and with the relative brightness variation of organizing in determined group during the observed temperature characteristic, comparative example 10 is 62.8% with respect to 200 ℃ of temperature, and embodiment 247 is 67.1 at uniform temp, shows higher numerical value.In addition, 300 ℃ with respect to 18.2% of comparative example 10, and embodiment 247 23.5% show higher numerical value.But this temperature profile represents to be provided with this nitride phosphor when the table of luminous element, can not change the composition of nitride phosphor and shows higher characteristics of luminescence person, and the temperature profile height of healing is then represented more stable.Confirm that by the result of table 32 nitride phosphor of the present invention is compared to comparative example 10, its temperature profile is better, and reliability is higher.Being compared to comparative example 10 and showing the very significantly characteristics of luminescence like this.Can reach the raising of the insurmountable characteristics of luminescence in the past thus very easily.
Embodiment 247～249.
The embodiment 247～249 of table 33 expression nitride phosphor of the present invention.In addition, the characteristics of luminescence of Figure 45 to 47 expression embodiment 247～249.Figure 45 is expression excites the luminescent spectrum of embodiment 247～249 o'clock with Ex=460nm figure.Figure 46 is the figure of the excitation spectrum of expression embodiment 247～249.Figure 47 is the figure of the reflection spectrum of expression embodiment 247～249.
Table 33 (1)
Raw material The result
The basic comprising element Raw material ratio of mixture (Ca/Si/Eu) Burn till pattern Atmosphere Medium particle diameter (Dm/ σ log) Medium particle diameter () (Dm/ σ log)
Embodiment 247 Ca 1.97Si 5N 8:Eu 0.03 1.97/5/0.03 1 stage, 1350 ℃ * 5h NH 3 5.33/0.410 4.69/0.378
Embodiment 248 Ca 1.99Si 5N 8:Eu 0.01 1.99/5/0.01 1 stage, 1350 ℃ * 5h NH 3 5.61/0.412 4.31/0.415
Embodiment 249 Ca 1.94Si 5N 8:Eu 0.06 1.94/5/0.06 1 stage, 1350 ℃ * 5h NH 3 5.13/0.366 4.67/0.419
Table 33 (2)
The characteristics of luminescence (460nm) Temperature profile
Tone x Tone y Brightness (%) Quantum yield (%) Peak wavelength (nm) 100℃ 200℃ 300℃
Embodiment 247 0.598 0.400 82.0 79.1 612 93.7 67.1 23.5
Embodiment 248 0.593 0.404 59.0 55.1 610 99.8 81.1 37.1
Embodiment 249 0.603 0.395 84.4 84.6 614 92.9 56.1 12.5
Embodiment 247～249th, check nitride phosphor L of the present invention XM YN (2/3X+4/3Y): the chemical property of R or the result of physical property.Nitride phosphor L XM YN (2/3X+4/3Y): R is (Ca 1-tEu t) 2Si 5N 8Embodiment 247～249th, Eu is used at activator R, and the cooperation ratio t of this Eu is changed.Embodiment 247 contains Eu0.015, and embodiment 248 contains Eu0.005, and embodiment 249 contains Eu0.03.Firing condition is identical with embodiment 247, heats up lentamente from room temperature, carries out burning till in 5 hours with about 1350 ℃, and is cooled to room temperature through 5 hours lentamente.
When embodiment 247 was compared to embodiment 248, temperature profile is higher to be very clear and definite.General employed luminous element is because till the temperature range of ascending temperature to 100～150 ℃, thus when nitride phosphor is formed on luminous element surperficial, this temperature range present stabilize to preferred.From this viewpoint, embodiment 248 is because temperature profile is fabulous, so have excellent technical meaning.
When embodiment 249 and embodiment 247 compared, then the former luminosity was higher, and quantum yield is also high.Therefore, implement to wait 249 and show the fabulous characteristics of luminescence.
Embodiment 250～252.
The embodiment 250～252 of table 34 expression nitride phosphor of the present invention.
Table 34
The basic comprising element Raw material ratio of mixture (Ca/Si/Eu) Burn till pattern Atmosphere Shape Body colour Visual luminous (365 nm)
Embodiment 250 Ca 1.8Si 5N 8: Eu 0.2 1.8/5/ 0.2 1 stage, 1350 ℃ * 5h NH 3 The BN boat Orange Orange
Embodiment 251 Ca 1.96Si 5N 8 :Eu 0.04 1.96/5/ 0.04 1 stage, 1350 ℃ * 5h NH 3 The BN boat Orange Orange
Embodiment 252 Ca 1.98Si 5N 8: Eu 0.02 1.98/5/ 0.02 1 stage, 1350 ℃ * 5h NH 3 The BN boat Orange Orange
The embodiment 250 of table 34 is Ca 1.8Si 5N 8: Eu 0.2The CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Mixture ratio (mol ratio), be adjusted to Ca: Si: Eu=1.8: 5: 0.03.
Ca 3N 2(high-purity chemical system) 1.243g
Si 3N 4(space portion system) 3.266g
Eu 2O 3(SHIN-ETSU HANTOTAI's system) 0.492g
These 3 kinds of raw materials of compound are fed into the BN crucible, under ammonia atmosphere, carry out burning till in 5 hours with tube furnace from 1200～1350 ℃.Temperature is to be heated to lentamente till 350 ℃ through 5 hours from room temperature, and after carrying out burning till in 5 hours, and then is cooled to lentamente till the room temperature through 5 hours.Ammonia continues circulation from start to finish with the ratio of 21/min.Its result, promptly can obtain body as orange, luminous also for orange nitride phosphor powder.In visual inspection, this fluorophor powder is that fluorophor powder all is orange luminescence.So, because that fluor all carries out equably is luminous, so providing and manufacturing cost cheap of the raising of making efficient, stable nitride phosphor can be provided.
Embodiment 251 is fluor Ca 1.96Eu 0.04Si 5N 8The CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Mixture ratio (mol ratio), be adjusted to Ca: Si: Eu=1.96: 5: 0.04.
Ca 3N 2(high-purity chemical system) 2.867g
Si 3N 4(space portion system) 6.923g
Eu 2O 3(SHIN-ETSU HANTOTAI's system) 0.208g
These 3 kinds of raw materials of compound are also to burn till with embodiment 250 identical test methods.Its result, identical with embodiment 250, it is orange can obtaining body colour, luminous also is orange fluorophor powder.
Embodiment 252 fluor Ca 1.985Eu 0.015Si 5N 8The CaCl2 Ca of raw material 3N 2, silicon nitride Si 3N 4, europium sesquioxide Eu 2O 3Mixture ratio (mol ratio), be adjusted to Ca: Si: Eu=1.98: 5: 0.02.
Ca 3N 2(high-purity chemical system) 2.916g
Si 3N 4(space portion system) 6.969g
Eu 2O 3(SHIN-ETSU HANTOTAI's system) 0.105g
These 3 kinds of raw materials of compound are also to burn till with embodiment 250 identical test methods.Its result, identical with embodiment 250, it is orange can obtaining body colour, luminous also is orange fluorophor powder.In addition, the nitride phosphor that obtains by present embodiment 252 is in visual inspection, and its luminosity more improves than comparative example.And then the luminosity that the light body of obtaining by present embodiment 252 shows and embodiment 251 is roughly the same.
(measurement result of the fluor that obtains by embodiment 251 and 252)
Carry out embodiment 251 and 252 nitride phosphor mensuration and as typical example.Test-results is shown in Figure 48 to Figure 51.Figure 48 is expression excites the luminescent spectrum of embodiment 251 and at 252 o'clock with Ex=00nm figure.Figure 49 is expression excites the luminescent spectrum of embodiment 251 and at 252 o'clock with Ex=460nm figure.Figure 50 is the figure of the reflectivity of expression embodiment 251 and 252.Figure 51 is the figure of the excitation spectrum of expression embodiment 251 and 252.
The visible region of wavelength 400nm is radiated at the nitride phosphor of embodiment 251 and 252.In Figure 48, embodiment 251 and 252 nitride phosphor can be luminous with 610nm.
With the rayed of the visible region of wavelength 460nm nitride phosphor in embodiment 251 and 252.In Figure 49, embodiment 251 can be luminous with 620nm, and embodiment 252 can be luminous with 610nm.So with respect to embodiment 252, embodiment 251 more can carry out red colour system because being offset to long wavelength side luminous.Since this 460nm be known blue series LED emission wavelength in, the highest wavelength of luminosity is so the combination by a blue and yellow red luminescent spectrum promptly can be made reddish white nitride phosphor.The nitride phosphor of reflectivity embodiment 252 is represented the higher reflection characteristic of nitride phosphor than embodiment 250.Embodiment 251 and any one nitride phosphor of 252 also absorb the light of the short wavelength side of visible region.Excitation spectrum is that the nitride phosphor of embodiment 251 shows the excitation spectrum higher than the nitride phosphor of embodiment 252.
Confirm the luminous of Huang-red visible region by this Figure 48～51.
Embodiment 253 and 254
Embodiment 253 is fluor Sr 1.97Eu 0.03Si 5N 8The cooperation ratio CaCl2 Ca of raw material 3N 2: silicon nitride Si 3N 4: europium sesquioxide Eu 2O 3=1.97: 5: 0.03.This 3 raw materials of compound is fed into the BN crucible, and burns till 3 hours with tube furnace and with 800～1000 ℃, after this, carries out burning till in 5 hours with 1250～1350 ℃, is cooled to lentamente through 5 hours till the room temperature.Ammonia is circulation constantly from start to finish with the ratio of 11/min.Its result, it is pink carrying out body colour, during the rayed of 365nm, promptly can obtain the luminous nitride phosphor of macroscopic pink colour system.During 200 ℃ of the nitride phosphor of embodiment 253 temperature profile 87.7%, and represent high temperature profile.The embodiment 253 and 254 of table 35 expression nitride phosphor of the present invention.
Table 35 (1)
Raw material
The basic comprising element The raw material ratio of mixture Burn till pattern Ambiance Shape Raw material (g)
Embodiment 253 Sr 1.97Si 5N 8: Eu 0.03 Sr/Si/Eu ＝1.97/5/0.03 2 stages, 800 ℃～1000 ℃ * 3h, 1250 ℃～1350 ℃ * 5h NH 3 The BN crucible 4.47
Embodiment 254 Sr 1.4Ca 0.6 Si 5N 8:Eu Sr/Ca/Si/Eu ＝1.26/0.54/5/0 .2 2 stages, 800 ℃～1000 ℃ * 3h, 1250 ℃～1350 ℃ * 5h NH 3 The BN crucible 8.8
Table 35 (2)
The result The characteristics of luminescence (460nm) Temperature profile (%)
Body colour Visual luminous (365 nm) Tone x Tone y Brightness (%) Energy efficiency (%) Quantum yield (%) 200℃
Embodiment 230 Peak value Peak value 0.625 0.373 58.4 62.4 62.9 87.7
Embodiment 231 Dense orange Reddish orange 0.663 0.336 35.5 81.3 86.7 92.3
Embodiment 254 is fluor Sr 1.4Ca 0.6Si 5N 8: Eu.Embodiment 254 is to burn till with embodiment 253 identical firing conditions.Figure 52 is the figure of the luminescent spectrum of expression when exciting embodiment 254 with Ex=460nm.Learn that by Figure 52 light time of luminescent spectrum of irradiation Ex=460nm when being compared to the Sr of independent use II valency, then more is offset to long wavelength side during the combination of Sr and Ca.The peak value 655nm of luminescent spectrum.During the fluor of combined blue based light-emitting device and embodiment 254, then can obtain the luminous fluor of reddish white color system therefrom.In addition, the fluor Sr of embodiment 254 1.4Ca 0.6Si 5N 8: the quantum yield 151.3% of Eu and very preferred.
Embodiment 255.
The light-emitting device of embodiment 255 is to use has the semiconductor light emitting raw material and the light-emitting device of type 2 of the nitride phosphor 8 of narration below that luminescent spectrum is the InGaN semiconductor layer of 460nm.
In the light-emitting device of the embodiment 255 that as above constitutes, has the light that blueness is a luminescent spectrum at semiconductor light-emitting elements, be the luminescent spectrum of the indirect that reflects with reflector and from semiconductor light-emitting elements and the luminescent spectrum that directly penetrates for being radiated at nitride phosphor 8, and penetrate as white light.In addition, by being fluor SrAl in nitride phosphor 8 doping greens 2O 4: Eu, Y 2SiO 5: Ce, Tb, MgAl 11O 19: Ce, Tb, Sr 7Al 12O 25: Eu, (Mg, Ca, Sr, Ba in more than at least 1) Ga 2S 4: Eu, blueness are light-emitting fluophor Sr 5(PO 4) 3Cl:Eu, (SrCaBa) 5(PO 4) 3Cl:Eu, (BaCa) 5(PO 4) 3Cl:Eu, (Mg, Ca, Sr, Ba in more than at least 1) 2B 5O 9Cl:Eu, Mn, (Mg, Ca, Sr, Ba in more than at least 1) (PO 4) 6Cl 2: Eu, Mn, red colour system light-emitting fluophor Y 2O 2S:Eu, La 2O 2S:Eu, Y 2O 3: Eu, Ga 2O 2S:Eu etc., the luminescent spectrum that can obtain to expect.
As the above light-emitting device that constitutes, its yield rate can be made with 99%.So, the light-emitting device of present embodiment is the fabulous light-emitting device of productivity, and the light-emitting device that reliability is higher and mottle is less can be provided.
Embodiment 256.
The light-emitting device 2 of the light-emitting device Class1 of embodiment 256, Figure 53 are the figure of luminescent spectrum of the light-emitting device of expression embodiment 256.Figure 54 is the tristimulus coordinates of the light-emitting device of expression embodiment 256.
The light-emitting device of embodiment 256 is to use to have the semiconductor light-emitting elements of luminescent spectrum that luminescent spectrum is 460nm and the nitride phosphor 8a of embodiment 247.
In this light-emitting device, when circulating current during at luminous element, then having the luminous element that peak wavelength is the luminescent spectrum of 460nm (blue led) carries out luminous, and this light is carried out the conversion of nitride phosphor 8a, and produce the different spectrographic light of light have and to absorb, all and to carry out reddish white color system luminous as light-emitting device therefrom.
Representing together among Figure 54 as the comparison of the light-emitting device of present embodiment 256 and using YAG is the measurement result of the light-emitting device of fluor.
The nitride phosphor 8a of the light-emitting device of present embodiment 256 use to mix the nitride phosphor, resin of some embodiment 247, gives the yttrium of agent alive with cerium. aluminium. and garnet is fluorescent substance (hereinafter referred to as YAG).This type of weight ratio, the nitride phosphor of portions of resin YAG: embodiment 247=25: 6: 3.On the other hand, blue semiconductor luminous element and YAG are the fluor of light-emitting device of the combination of fluor, are with portions of resin YAG=25: 6 weight ratio and mixing.It is semiconductor light-emitting elements 1 with InGaN semiconductor layer of 460nm (below, be called blue led) that the light-emitting device of present embodiment 256 is to use luminescence peak.With the luminous conversion of carrying out nitride phosphor 8a of blue led, promptly can obtain to carry out the luminous light-emitting device of reddish white color system 2.
With the light-emitting device of present embodiment 256 with to use blue led and YAG be that the light-emitting device of fluor compares.This YAG is that fluor is 463.47nm with respect to peak wavelength, and the peak wavelength of nitride phosphor 8a has luminescent spectrum in the position different with 596.00nm.In tristimulus coordinates, using YAG is the light-emitting device of the comparative example of fluor, is with tone x=0.348, the white of the comparatively blue white hair light that tone y=0.367 is represented.On the other hand, using the light-emitting device 2 of the embodiment 256 of nitride phosphor 8a, is with tone x=0.454, the reddish white that tone y=0.416 is represented.The colour temperature 2827.96K of the light-emitting device of embodiment 256, and have the characteristics of luminescence near the bulb look.In addition, in color developing, use the light-emitting device 2 of nitride phosphor 8a, expression and use YAG are the roughly the same color developing of light-emitting device of fluor.And then light-emitting device 2 of the present invention has the high-luminous-efficiency of 24.871m/W.
Below, intersection compares example and the embodiment that relates to embodiments of the present invention 7 is described in detail in detail.Also have, the present invention has more than and is limited to embodiment shown below.
(embodiment 257)
Shown in Figure 55, in this comparative example 11 to 13 and the photodiode 200 that forms, the photodiode that possesses the guiding type that lead-in wire 205 and inner lead 206 are installed, in the cup portion that lead-in wire 205 is installed, be mounted with led chip 202, and in cup portion can cover the state of led chip 202, and filling contains after the coating portion 201 of the fluor that makes up as following table 37, constitutes by modular unit 204 resin mold blockings.Herein, the n lateral electrode of led chip 202 and p lateral electrode are used lead 203 respectively and are connected lead-in wire 205 and inner lead 206 are installed.
Figure 57 represents that the employed YAG of present embodiment is the absorption spectrum that excites of fluor.In addition, Figure 58 represents that the employed YAG of present embodiment is the luminescent spectrum of fluor.Present embodiment uses (Y respectively 0.8Gd 0.2) 3Al 5O 12: Ce (hereinafter referred to as " fluor 257-1 "), Y 3Al 5O 12: Ce (hereinafter referred to as " fluor 257-2 ") and Y 3(Al 0.8Ga 0.2) 5O 12: Ce (hereinafter referred to as " fluor 257-3 ") and be fluor as forming different YAG.This type of fluor is to absorb from the blueness system of led chip and exciting light and the light of yellow system to green system is carried out luminous fluor.
Figure 59 represents the absorption spectrum that excites of the employed nitride phosphor of present embodiment.In addition, Figure 60 represents the luminescent spectrum of the employed nitride phosphor of present embodiment.Present embodiment uses (Ca respectively 0.985Eu 0.015) 2Si 5N 8(hereinafter referred to as " fluor 257-4 ") and (Sr 0.679Ca 0.291Eu 0.03) 2Si 5N 8(hereinafter referred to as " fluor 257-5 ") and as forming different nitride phosphors.This type of fluor absorbs from the blueness system of led chip and excites, and the light of redness is carried out below the luminous fluor, represents the composition of above-mentioned fluor and the peak wavelength of luminescent spectrum.
Table 36
Form Peak luminous wavelength [nm] Tone x Tone y
Fluor 257-1 (Y 0.8Gd 0.2) 3Al 5O 12:Ce 562 0.457 0.527
Fluor 257-2 Y 3Al 5O 12:Ce 550 0.422 0.554
Fluor 257-3 Y 3(Al 0.8Ga 0.2) 5O 12:Ce 533 0.383 0.575
Fluor 257-4 (Ca 0.986Eu 0.015) 2Si 5N 8 610 0.597 0.401
Fluor 257-5 (Sr 0.679Ca 0.291Eu 0.03) 2Si 5N 8 637 0.638 0.36
At first, fluor 257-1 is respectively used a kind and form after the photodiode to fluor 257-5, surrounding temperature is risen, and measure luminous output with respect to the photodiode of surrounding temperature.Then, relate to fluor 257-1 to fluor 257-5, try to achieve respectively with 25 ℃ be the luminous relative output of LED of benchmark, and be shown in Figure 64 to Figure 68 as surrounding temperature one relative bright dipping force characteristic.In addition, when the surrounding temperature of photodiode is carried out 1 ℃ variation, try to achieve the rate of descent of the luminous relative output of LED that relates to each fluor, be shown in following table 37 as the luminous output reduced rate that rises with respect to the temperature of the 1st fluor and the 2nd fluor.
Table 37
Form Luminous output reduced rate [a.u./℃]
Fluor 257-1 (Y 0.8Gd 0.2) 3Al 5O 12:Ce 2.2×10 -3
Fluor 257-2 Y 3Al 5O 12:Ce 1.5×10 -3
Fluor 257-3 Y 3(Al 0.8Ga 0.2) 5O 12:Ce 1.8×10 -3
Fluor 257-4 (Ca 0.986Eu 0.015) 2Si 5N 8 3.4×10 -3
Fluor 257-5 (Sr 0.679Ca 0.291Eu 0.03) 2Si 5N 8 1.9×10 -3
In the present embodiment, excited fluophor and the led chip 202 that uses, with the luminous element that the InGaAIN compound semiconductor forms as luminescent layer, the peak wavelength 460nm of its luminescent spectrum.In addition, by current density is increased to 3～300A/cm 2Between, make tristimulus coordinates be offset to low colour temperature side along the blackbody radiation track.Figure 56 is the figure that expression will be flowed the current characteristics of the luminescent spectrum of electricity when the electric current of led chip 202 changes.Shown in Figure 56, the current characteristics of luminescent spectrum imports electric current along with increasing to throw, and peak wavelength shift is to short wavelength side.
So, shown in Figure 57, the increase of the electric current by being directed into led chip, and, above-mentioned 3 fluor 257-1 to 257-3 are excited the big transformation of the way in position of the peak wavelength of absorption spectrum do consistent in the peak wavelength of the luminescent spectrum of led chip position for skew.Herein, be preferred below the difference 40nm of the peak wavelength of the luminescent spectrum of sharp length of the peak value that excites absorption spectrum of fluor 257-1 to 3 and led chip.By using such fluor, because the launching efficiency of this fluor promptly improves, and need not wavelength conversion can reduce light quantity, so can prevent the chroma offset of light-emitting device from the LED bright dipping.
Herein, when using fluor 257-3, the luminescent spectrum of fluor 257-3 more moves to short wavelength side than the luminescent spectrum of fluor 257-1 shown in Figure 58.Therefore, by with YAG being the peak skew that excites absorption spectrum of fluor, can prevent light-emitting device luminous of the chroma offset of light-emitting device, because of departing from from the blackbody radiation track, so by increasing fluor 257-4 or fluor 257-5, promptly red composition can be attached to mixed light, and tristimulus coordinates is adjusted near the blackbody radiation track.
Will with respect to YAG be fluor nitride phosphor blending this be shown in following table 38.
Table 38
Embodiment No. Fluor Resin The YAG fluor Nitride phosphor
Embodiment 257-1 Fluor 3+ fluor 5 10 2.6 0.4
Comparative example 11 Fluor 1 10 3 0
Comparative example 12 Fluor 2+ fluor 4 10 2.2 0.4
Comparative example 13 Fluor 2+ fluor 5 10 2.2 0.4
The measurement result of the optical characteristics when embodiment 257 and comparative example 11 are formed photodiode in 13 is represented following table 39.
Table 39
Embodiment No. Along directional current [mA] Along directional current [V] Radiation beam [mW] Light beam [lm] Tone x Tone y Correlated colour temperature [K] Number Ra is estimated in average colour developing Lamp efficiency [lm/W]
Embodiment 257-1 20 3.7 7.0 2.04 0.332 0.348 5504.5 85.5 27.5
Comparative example 11 20 3.7 9.4 2.83 0.332 0.330 5523.6 82.0 38.0
Comparative example 12 20 3.8 8.4 2.54 0.332 0.329 5495.7 83.6 33.7
Comparative example 20 3.7 8.3 2.34 0.333 0.317 5462.7 87.9 31.2
13
Shown in table 39, the color developing of embodiment 257 and comparative example 13, its Ra all forms more than 85, is compared to other comparative example and more can improves color developing.In addition, Figure 61 is that expression relates to embodiment 257 and comparative example 11 to 13, the figure that it changes with respect to the colourity of surrounding temperature.Shown in Figure 61, the equal Yin Wendu of each of embodiment 257 and comparative example 11 to 13 rises and colourity is changed toward the thick direction of arrow among the figure.
Figure 62 is that expression relates to embodiment 257 and this than example 11 to 13, the figure that changes with respect to the colourity of the pulsed current that is directed into led chip.In the present embodiment, be attached to led chip by pulsed current with 1～100mA (1,5,10,20,40,60,80,100mA), and under the condition of the heating that can ignore led chip, and confirm the current characteristics of additional red composition at the LED of White LED.Shown in Figure 62, during situation, import electric current, and colourity can be from the blackbody radiation track and move to the high luminance relay temperature province away from the state of the direction of arrow along with increasing from comparative example 11 to comparative example 13.On the other hand, during the situation of embodiment 257, can learn colourity with can be roughly along the state of blackbody radiation track, move in low colourity side toward the direction of arrow.
Figure 63 is that expression relates to embodiment 257 and comparative example 11, the figure that the colourity when carrying out the DC driving changes.During the situation of comparative example 11, when increasing the electric current of 1mA to 5mA, 10mA, 20mA, 40mA, 60mA, the colourity of its each current value is with can be from the blackbody radiation track and move to the high chroma side away from the state of the direction of arrow.On the other hand, during the situation of embodiment 257, it makes the colourity of light produce change because of colour mixture, and on chromaticity diagram, the X coordinate is 0.326 to 0.333, and the Y coordinate is in 0.343 to 0.348 scope.Also promptly, during the situation of embodiment 257, the colourity of the light that produces because of colour mixture even increase electric current, is also roughly moving along the position of blackbody radiation track, and is producing the variation of colourity hardly.So, during the situation of embodiment 257, colourity changes generation hardly, its result shows, change along the blackbody radiation track shown in Figure 61 toward the colourity of high chroma side as surrounding temperature one colourity characteristic, and as importing electric current one colourity characteristic colorimetric properties along the blackbody radiation track shown in Figure 62 toward low colourity side and colourity variation along the blackbody radiation track shown in Figure 62 toward low colourity side is cancelled each other.
The formation of embodiment 257 and at the luminous output rate of descent of surrounding temperature of the fluor of combination all 2.0 * 0 -3Other following fluor to embodiment of [a.u/ ℃] is compared comparatively littler, and and luminous output rate of descent differ from 2.0 * 10 -4The embodiment of other of [a.u/ ℃] compares comparatively littler and combination person.Also promptly, the luminous output of rising with respect to the degree of 3 and the fluor 5 of fluor is fallen rate about equally.By taking such formation, even then cause the rising of spending on every side because of the heating of luminous element, and the luminous output of each of fluor 3 and fluor 5 produces when descending, and then the luminous output of fluor 3 and fluor 5 is poor, is not subjected to the influence of surrounding temperature and almost maintains identical value.Also be, by taking formation of the present invention, promptly can be not because of the surrounding temperature of light-emitting device, the particularly variation of the surrounding temperature of the light-emitting device that produces because of the variation of electric current, color developing can be improved, and the light-emitting device that produces chroma offset hardly can be made.In addition, with the present invention to light-emitting device and will be from this light-emitting device and the light of bright dipping is directed into the light guiding plate combination of luminous inspection surface side, form spendable cloudy irradiation light source and during as the component parts of liquid-crystal display, promptly can be not because of around variation of temperature improve color developing, and can make the back light that produces chroma offset hardly.(embodiment 258,259)
Behind present embodiment, be the combination of fluor and nitride phosphor with YAG, and form the light that can make warm colour system, also be that (light of colour temperature 2500K～3800K) carries out luminous light-emitting device in so-called bulb look zone.The employed YAG of present embodiment is composition formula, the peak luminous wavelength λ p[nm of fluor (fluor 258-1,258-2) and nitride phosphor (fluor 258-3,258-4)] and tone shown in following table 40.
Table 40
Form Peak luminous wavelength λ p[nm] Tone x Tone y
Fluor 258-1 (Y 0.2Gd 0.8) 2.965Ce 0.035Al 5O 12 582 0.495 0.495
Fluor 258-2 Y 2.965Ce 0.035(Al 0.8Ga 0.2) 5O 12 537 0.386 0.573
Fluor 258-3 (Ca 0.97Eu 0.03) 2Si 5 N 8 610 0.593 0.399
Fluor 258-4 (Sr 0.475Ca 0.475Eu 0.03Mn 0.02) 2Si 5 N 8 650 0.643 0.348
In addition, the luminous output rate of descent of and each fluor measured identical with embodiment 257 [a.u./℃], shown in following table 41.
Table 41
Form Luminous output reduced rate [a.u./℃]
Fluor 258-1 (Y 0.2Gd 0.8) 2.965Ce 0.035Al 5O 12 5.07×10 -3
Fluor 258-2 Y 2.965Ce 0.035(Al 0.8Ga 0.2) 5O 12 2.00×10 -3
Fluor 258-3 (Ca 0.97Eu 0.03) 2Si 5N 8 2.93×10 -3
Fluor 258-4 (Sr 0.475Ca 0.475Eu 0.03Mn 0.02) 2Si 5N 8 2.70×10 -4
Present embodiment is with the weight ratio shown in the following table 42, forms light-emitting device with resin, fluor 258-2 and fluor 258-3 and fluor 258-4 combination and embodiment 257 same treatment respectively, and makes the luminous of feasible bulb look.
Table 42
Embodiment No. Fluor Resin The YAG fluor Nitride phosphor
Embodiment 258 Fluor 7+ fluor 8 10 3.8 0.912
Embodiment 259 Fluor 7+ fluor 9 10 5.0 0.900
Comparative example 14 Fluor 6 10 10
The measurement result of the optical characteristics of formed light-emitting device among embodiment 258 and the embodiment 259 is shown in following table 43.
Table 43
Embodiment No. Along directional current [mA] Along directional current [V] Radiation beam [mW] Light beam [lm] Tone x Tone y Correlated colour temperature [K] Number Ra is estimated in average colour developing Lamp efficiency [lm/W]
Embodiment 258 20 3.22 4.6 1.488 0.451 0.408 2810.9 72.5 23.1
Embodiment 259 20 3.24 4.1 1.130 0.450 0.409 2836.7 85.7 17.4
Comparative example 14 20 3.23 3.8 1.209 0.448 0.408 2854.8 65.2 18.7
Figure 73 is that expression relates to embodiment 258 and embodiment 259, the figure of the variation of the colourity when carrying out the DC driving.During the situation of the following comparative example of narrating 14, with electric current when 1mA increases to 5mA, 10mA, 20mA, 40mA, 60mA, the colourity of its each current value and blackbody radiation track cross and move to the high luminance relay temperature side.On the other hand, during the situation of embodiment 258 and enforcement looks 259, import electric current and also almost change of colourity even change.The formation of embodiment 258 and embodiment 259 all makes 3.0 * 10 to the luminous output rate of descent of surrounding temperature at the fluor of combination -3Below [a.u/ ℃], and littler with the fluor 258-1 of comparative example 14.According to formation of the present invention, the surrounding temperature of no matter luminous part then, particularly because of the surrounding temperature of the fluor that variation produced of electric current as where changing, and chroma offset also can produce hardly, and can make the light-emitting device that improves color developing.
Separately the YAG shown in the use table 40 is that fluor 258-1 and the above embodiments 258,259 similarly form and can carry out the luminous light-emitting device of bulb colour system and as a comparative example 14.Herein, the resin of this comparative example and the weight ratio of fluor are shown in the table 42.In addition, with as a comparative example 14 and the measurement result of the optical characteristics of the light-emitting device that forms, in the table 43 under all being shown in embodiment 258,259.And then in Figure 73, represent the variation of the colourity when relating to comparative example 14 carries out the DC driving.The light-emitting device of this comparative example shown in Figure 73 figure, be with electric current when 1mA increases to 5mA, 10mA, 20mA, 40mA, 60mA, the then colourity of each current value and blackbody radiation track cross and move to high colour temperature side.This be because the peak luminous wavelength of led chip shown in Figure 56, move to short wavelength side along with the increase of electric current, and from the peak wavelength that excites absorption spectrum of the fluor 258-1 shown in Figure 69 and depart from, so can be considered the wavelength conversion decrease in efficiency of fluor, and from the more cause of light wavelength composition of not carrying out the led chip of wavelength conversion because of fluor.On the other hand, the peak wavelength that excites absorption spectrum of embodiment 258 and embodiment 259 employed fluor 258-2, owing to the peak wavelength than fluor 258-1 is a short wavelength side, and the peak luminous wavelength of led chip, is descending so the wavelength conversion efficient of fluor is unlikely in the mobile scope according to the variation that imports electric current.And then make the measure that is used in combination by the peak wavelength that it is excited absorption spectrum for nitride phosphor and YAG fluorescence in the peak luminous wavelength of the led chip scope mobile when implementing the situation of looks 258 and embodiment 259 according to the variation that imports electric current, no matter can make the surrounding temperature of the luminous element that the variation because of electric current produces changes, also promptly how without the variation of the surrounding temperature of fluor, the sight that also produces chroma offset hardly resembles, and can carry out the luminous light-emitting device of bulb colour system that color developing improves.
(embodiment 260)
In the present invention, except the YAG shown in table 36 and the table 40 be fluor, be Y with the composition formula 2.965Ce 0.035(Al 1-XGa X) 5O 12In, at random be formed on the fluor of replacing in the scope of 0＜X≤0.8, and relate to the replacement of Gd, be at general formula (Y 1-YGd Y) 2.965Ce 0.035Al 5O 12In, the fluor that at random is formed on＜X≤replaces in 0.9 the scope.In addition, at general formula Y 3-ZCe ZAl 5O 12In, in the scope of 0.015≤Z≤0.600, at random form fluor.
With the above embodiments 257～259 in the same manner, by fluor and the nitride phosphor that suitably makes up present embodiment 260, and produce the chroma offset phenomenon hardly, and can make the luminous light-emitting device of the tone that improves color developing and can expect.
Below, the embodiment that relates to embodiments of the present invention 8 is described in detail in detail.Also have, the present invention not only is limited to embodiment as follows certainly.
(embodiment 261)
Figure 74 is shown in the present embodiment and the mode chart of the photodiode 300 that forms.In present embodiment 261, contain nitride based fluor (Sr at the 1st luminescent coating 303 0.7Ca 0.3) 2Si 5N 8: Eu (hereinafter referred to as " fluor 261-1 ").Figure 84 represents the absorption spectrum that excites of this fluor, and Figure 85 represents luminescent spectrum.In addition, containing at the YAG of the 2nd luminescent coating 306 is fluor Y 3(Al 0.8Ga 0.2) 5O 12: Ce (hereinafter referred to as " fluor 261-2 ").Figure 82 represents the absorption spectrum that excites of this fluorescence sound, and Figure 83 represents luminescent spectrum.
Shown in Figure 74, thermoplastic resin is formed the encapsulation 308 with the 1st recess the 301, the 2nd recess 305 and positive and negative a pair of lead-in wire electrode 309 as material and by ejection formation.Can carry out the luminous led chip 302,304 of the light of blue region respectively then also fixes in the 1st recess and the 2nd recess by the insulativity caking agent.In the present embodiment, though the led chip that will be loaded in each recess is made 1 chip respectively, also a plurality of chips can be loaded in each recess.So, can directly excite the fluor in each recess, so can form the light-emitting device that can carry out high brightness luminescent by loading a plurality of led chips.Use conducting wire 110 and with the positive electrode of led chip 302,304 and negative potential respectively lead be bonded on the positive electrode and the negative potential of lead-in wire electrode.
To contain the formation material adjustment of fluor 261-1, and dispose modulated material, and carry out solidification treatment with the state that can cover the led chip 302 that is loaded in the 1st recess at the 1st luminescent coating 303 of silicone resin.Herein, the blend ratio (silicone resin) of silicone resin and fluor 261-1: (fluor 261-1)=10: 3 (weight ratio).
Then, will contain fluor 261-2 and modulate at the formation material of the 2nd luminescent coating 306 of silicone resin, and can covering the led chip 304 that is loaded in the 2nd recess and the modulated material of state configuration of the 1st luminescent coating 303, and carry out solidification treatment.Herein, the blend ratio (silicone resin) of silicone resin and fluor 261-2: (fluor 261-2=10: 1 (weight ratio).
By making diffusant contain measure, and conducting wire 309, luminescent coating and LED are got the sheet sealing at the modular unit 307 of silicone resin.
Circulating current promptly can be obtained the mixed light with luminescent spectrum shown in Figure 79 when as above formed light-emitting device, and is compared to prior art and more improves color developing, and can carry out high output light emitting.Herein, the output of led chip 302 is more greatly preferred than the output of led chip 304.Then more its color developing can be improved by processing like this, and high output light emitting can be carried out.The measurement result of the optical characteristics when forming photodiode in the present embodiment is shown in following table 44.
Table 44
Embodiment No. Tone x Tone y Colour temperature [K] Color developing Ra Special color developing R9
Embodiment 261 0.361 0.344 4380 91.9 91.4
With light-emitting device of the present invention with will send the light of light by this light-emitting device, guide to the light guiding plate combination of luminous inspection surface side, and when forming the back light can be used as the component parts of liquid-crystal display and to use, promptly no matter how the changing conditions of surrounding temperature can improve its color developing, and can make the back light that produces chroma offset hardly.
(embodiment 262)
Figure 75 is the mode chart that is shown in formed photodiode 400 in the present embodiment.In the present embodiment, as above-mentioned embodiment, and on the recess 301 that is provided with not at the 1st recess and the 2nd recess, at least load a led chip 302, and, on led chip 302, stack gradually the 1st luminescent coating and the 2nd luminescent coating according to the method identical with embodiment 261.By taking such formation, be compared to prior art and more can make the light-emitting device that improves color developing.
(embodiment 263)
In the present embodiment, contain similarly, be respectively fluor 261-1 and fluor 261-2 at the fluor of the 1st luminescent coating 303 and the 2nd luminescent coating 306 and the foregoing description.But, the amount of fluor 261-1 and fluor 261-2, the amount than the foregoing description is more respectively.The 1st luminescent coating forms with the 2nd luminescent coating basis method identical with the foregoing description.
Figure 76 is the mode chart that is shown in formed photodiode 300 in the present embodiment.Photodiode 300 is the photodiodes that possess the leading type that lead-in wire 402 and inner lead 401 are installed, and it is provided with the 1st recess 301 and the 2nd recess 305 in the cup portion that lead-in wire 402 is installed.The bottom surface of this recess is provided with led chip 302, and is formed with the 1st luminescent coating 303 with the state that can cover this led chip 302.In addition, the bottom surface of the 2nd recess is provided with led chip 304, and is formed with the 2nd luminescent coating 306 with the state that can cover this led chip 304 and the 1st luminescent coating 303.And then luminescent coating, lead-in wire electrode and conducting wire constitute by modular unit 307 resin mold blockings.Herein, the lateral electrode of led chip 302,304 and p lateral electrode are used lead 110 and are connected to installation lead-in wire 402 and inner lead 401.
At established light-emitting device, promptly can obtain the reddish mixed light shown in Figure 79 by circulating current, and be compared to prior art and more can improve its color developing with luminescent spectrum.Optical measurement result when forming photodiode in the present embodiment is shown in following table 45.
Table 45
Embodiment No. Tone x Tone y Colour temperature [K] Color developing Ra Special color developing R9
Embodiment 263 0.428 0.411 3199 95.6 78.2
(embodiment 264)
Figure 77 is the mode chart that is shown in formed photodiode 400 in the present embodiment.In the present embodiment with embodiment 263 in the same manner, on the recess 301 that forms with respect to the lead-in wire electrode is installed, loading a led chip 302 at least.According to the method identical, the 1st luminescent coating and the 2nd luminescent coating on led chip 302, have been stacked gradually with other above-mentioned embodiment.Compared with prior art can make the light-emitting device that improves color developing by taking such formation.
(embodiment 265)
Figure 78 is shown in formed photodiode 300 and mode chart in the present embodiment.Similarly be provided with other embodiment:
The 1st recess 301, it is mounted with the led chip 302 that is covered by the 1st luminescent coating 303; And
The 2nd recess 305, it is mounted with the led chip 304 that is covered by the 2nd luminescent coating 306.
Wherein, formed in the present embodiment photodiode 300 is provided with a pair of positive and negative a pair of lead-in wire electrode 309 respectively to led chip 302,304, and respectively electric current is directed into led chip 302,304 and makes the control can independently carry out luminous output.
Like this will carry out wavelength conversion and the measure of the colour mixture extent control of the light of bright dipping according to the 1st fluor and the 2nd fluor, can make the light-emitting device that can be selected from by the colour temperature of regulating mixed light.
(embodiment 266)
Figure 74 is the mode chart that is shown in formed photodiode 300 in the present embodiment.In the present embodiment, the nitride phosphor that contains at the 1st luminescent coating 303 is (Sr 0.7Ca 0.3) 2Si 5N 8: Eu (hereinafter referred to as " fluor 261-1 ").In addition, containing at the YAG of the 2nd luminescent coating 306 is that fluor is Y 3(Al 0.8Ga 0.2) 5O 12: Ce (hereinafter referred to as " fluor 261-2 ").
Shown in Figure 74, thermoplastic resin is formed the encapsulation 308 with the 1st recess the 301, the 2nd recess 305 and positive and negative a pair of lead-in wire electrode 309 as material and according to ejection formation.Can carry out the luminous led chip 302,304 of the light of blue region respectively then also fixes in the 1st recess, the 2nd recess by the insulativity caking agent.In the present embodiment, the led chip that is loaded in each recess is made 1 chip respectively, but also a plurality of chips can be loaded in each recess.Like this pass through to load a plurality of chips owing to can directly excite the fluor in each recess, so but can form high brightness ground and carry out luminous light-emitting device.The positive electrode and the negative potential that use conducting wire 310 and respectively the positive electrode and the negative potential lead of led chip 302,304 is bonded on the lead-in wire electrode.
Figure 82 represents that the employed YAG of present embodiment is the absorption spectrum that excites of fluor.In addition, Figure 83 represents that the employed YAG of present embodiment is the luminescent spectrum of fluor.Present embodiment uses Y 3(Al 0.8Ga 0.2) 5O 12: Ce (fluor 261-2), (Y 0.8Gd 0.2) 3Al 5O 12: Ce (hereinafter referred to as " fluor 266-1 ") and Y 3Al 5O 12: Ce (hereinafter referred to as " fluor 266-2 ") and to form different YAG as each be fluor.This type of fluor absorbs from the blueness system of led chip and excites, and yellow to green light is carried out luminous fluor, and contains at the 2nd luminescent coating.
Figure 84 represents the absorption spectrum that excites of the employed nitride phosphor of present embodiment.In addition, Figure 85 represents the luminescent spectrum of the employed nitride phosphor of present embodiment.Present embodiment uses (Sr 0.7Ca 0.3) 2Si 5N 8: Eu (fluor 261-1), Ca 2Si 5N 8: Eu (hereinafter referred to as " fluor 266-3 ") and form different nitride phosphors as each.This type of fluor absorbs from the blueness system of led chip and excites, and the light of redness is carried out luminous fluor, and contains at the 1st luminescent coating.Below, show the composition of employed fluor in the present embodiment and the peak wavelength and the tone of luminescent spectrum.
Table 46
Form Luminous spike wavelength X p[nm] Tone x Tone y
Fluor 261-1 (Sr 0.7Ca 0.3) 2Si 5N 8:Eu 637 0.638 0.360
Fluor 261-2 Y 3(Al 0.8Ga 0.2) 5O 12:Ce 533 0.383 0.575
Fluor 266-1 (Y 0.8Gd 0.2) 3Al 5O 12:Ce 562 0.457 0.527
Fluor 266-2 Y 3Al 5O 12:Ce 550 0.422 0.544
Fluor 266-3 Ca 2Si 5N 8:Eu 610 0.597 0.401
At first, fluor 261-1 is used per a kind and form after the photodiode to fluor 266-3, under the condition of the heating that can ignore led chip itself, surrounding temperature is risen by the pulsed current that increases 20mA, and measure the luminous output of sending out disome with respect to surrounding temperature.Then, respectively at fluor 261-1 to fluor 266-3, try to achieve with 25 ℃ be the luminous relative output of LED of benchmark, and as surrounding temperature one light output characteristic and be shown in Figure 87 to Figure 91 relatively.In addition, the surrounding temperature of photodiode is being carried out 1 ℃ when changing, to trying to achieve the rate of descent of the luminous relative output of LED at each fluor, and, be shown in the following table 47 as luminous output rate of descent with respect to the rising of surrounding temperature.
Table 47
Be coated in the fluor of light-emittingdiode Form Luminous output reduced rate [a.u./℃]
Fluor 261-1 (Sr 0.7Ca 0.3) 2Si 5N 8:Eu 1.9×10 -3
Fluor 261-2 Y 3(Al 0.8Ga 0.2) 5O 12:Ce 1.8×10 -3
Fluor 266-1 (Y 0.8Gd 0.2) 3Al 5O 12:Ce 2.2×10 -3
Fluor 266-2 Y 3Al 5O 12:Ce 1.5×10 -3
Fluor 266-3 Ca 2Si 5N 8:Eu 3.4×10 -3
Employed fluor in the present embodiment is the luminous output rate of descent that rises with respect to temperature is about equally fluor 261-1 and fluor 261-2.Also promptly, the luminous output rate of descent with respect to the surrounding temperature of the fluor that has made up is 2.0 * 10 -3[a.u./℃] following to be compared comparatively forr a short time with the combination of other fluor, and the difference of luminous output rate of descent is 2.0 * 10 -4[a.u./℃] compare comparatively littler combination person with the combination of other fluor.
At the led chip 302 or 304 that present embodiment uses in order to excited fluophor, be the luminous element that the InGaAlN compound semiconductor is formed as luminescent layer, near the peak wavelength 460nm of its luminescent spectrum.In addition, by current density is increased to 3～300A/cm 2, then tristimulus coordinates is offset to low colour temperature side along the blackbody radiation track.Figure 81 represent to circulate figure of current characteristics of the luminescent spectrum when the electric current of led chip 302,304 changes.Shown in Figure 81, the current characteristics of luminescent spectrum makes peak wavelength shift to short wavelength side along with increasing the importing electric current.
So, shown in Figure 82, the increase of the electric current by being directed into led chip, and on the position of peak wavelength for skew of the luminescent spectrum of led chip is roughly made unanimity with the position of the peak wavelength that excites absorption spectrum of above-mentioned 3 fluor 261-2,266-1,266-2.Herein, the difference 40nm of the peak wavelength of the luminescent spectrum of the peak wavelength that excites absorption spectrum of fluor 261-2,266-1,266-2 and led chip is following for preferred.By using such fluor, owing to the launching efficiency that improves this fluor, and need not can reduce the light quantity of sending light from LED by wavelength conversion, so can prevent the chroma offset phenomenon of light-emitting device.
Herein, when using fluor 261-2, the luminescent spectrum of fluor 261-2 more moves to short wavelength side than the luminescent spectrum of other fluor shown in Figure 82.Therefore, by with YAG being the measure of the peak skew that excites absorption spectrum of fluor, then the luminous of light-emitting device owing to the chroma offset that can prevent light-emitting device departs from from the blackbody radiation track, so by increasing fluor 261-1 or fluor 266-3, promptly can add red composition at mixed light, and tristimulus coordinates can be adjusted near the blackbody radiation track.
Shown in table 44, during the situation of present embodiment, its color developing forms Ra=91.9, and is compared to prior art and more can improves color developing.
Figure 86 is shown in formed light-emitting device in the present embodiment, the figure that its colourity of carrying out the DC driving changes.With current density from 15[A/cm 2] increase to 180[A/cm 2] time, the colourity change of colour mixture and the light that produces on chromaticity diagram in, the X coordinate is in 0.339 to 0.351 scope, and the Y coordinate is in 0.321 to 0.322 scope.Also promptly, even colour mixture and the colourity of the light that produces increases electric current also roughly moves along the position of blackbody radiation track, and produces the variation of colourity hardly.
The formation of present embodiment is 2.0 * 10 with respect to the luminous output rate of descent of the surrounding temperature of the fluor that has made up -3[a.u./℃] following to be compared comparatively forr a short time with the fluor of other embodiment, and the difference of luminous output rate of descent is 2.0 * 10 -4[a.u./℃] compare comparatively littler combination person with other embodiment.Also promptly, the luminous output rate of descent that rises with respect to the temperature of fluor 261-1 and fluor 261-2 about equally.By taking such formation, even the rising of the surrounding temperature that is produced because of heating of luminous element etc., and each luminous being output as when descending of fluor 261-1 and fluor 261-2, and the luminous output of fluor 261-1 and fluor 261-2 is poor, is not subjected to the influence of surrounding temperature and maintains much at one value.Also promptly, by taking the formation of present embodiment, then no matter how the variation of the surrounding temperature of light-emitting device can improve color developing, and can make the light-emitting device that produces chroma offset hardly.
In addition, with light-emitting device of the present invention and will be from this light-emitting device and the light of bright dipping is directed into the light guiding plate combination of luminous inspection surface side, and when forming the back light can be used as the component parts of liquid-crystal display and to use, no matter variation that promptly can surrounding temperature how, color developing can both be improved, and the back light that produces chroma offset hardly can be made.
The possibility of utilizing on the industry
According to the present invention, namely can be with combinations such as blue series light-emitting components and use, and have luminescent spectrum at yellow to red area, and luminous efficiency and the higher fluorophor of durability can be provided.
In addition, by utilizing this type of fluorophor, the white color system light-emitting device that the reddish warm colour that the luminous efficiency excellence namely can be provided is.
Also namely, has the meaning that to make near the very important technical elements of the light-emitting device of bulb look.

Claims (35)

1. fluor, its absorption has at least a portion of the light of the 1st luminescent spectrum, and sends the light with 2nd luminescent spectrum different with described the 1st luminescent spectrum; It is characterized in that it is the silicon nitride that contains the Sr-Ca-Si-N:R base that is added with Mn, wherein R is at least a or multiple rare earth element, and wherein Eu is necessary.
2. fluor according to claim 1; It also contains O.
3. according to 2 described fluor of claim the; Wherein based on the total amount of composition, the content of described O is 3 weight % or lower.
4. fluor according to claim 1; It also contains the element among at least a or multiple Mg of being selected from, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni.
5 fluor according to claim 1; The mol ratio Sr of Sr and Ca: Ca=1 to 9 wherein: 9 to 1.
6. according to the fluor of claim 1; The mol ratio Sr of Sr and Ca: Ca=1 wherein: 1.
7. fluor according to claim 1; Wherein based on Sr-Ca, Sr and Ca, the use level of Eu in described fluor is in 0.003 to 0.5mol scope.
8. fluor according to claim 1; Wherein based on Sr-Ca, Sr and Ca, the amount of described Eu in described fluor is in 0.005 to 0.1mol scope.
9. fluor according to claim 1; Wherein based on Sr-Ca, Sr and Ca, the content in the described fluor of Mn is in 0.001 to 0.3mol scope.
10. fluor according to claim 1; Wherein based on Sr-Ca, Sr and Ca, the content in the described fluor of Mn is in 0.0025 to 0.03mol scope.
11. fluor according to claim 1; Its median size is 3 μ m or bigger.
12. fluor according to claim 1; The content of wherein said Mn is 5000ppm or lower.
13. a fluor absorbs at least a portion of the light with the 1st luminescent spectrum, and sends the light with 2nd luminescent spectrum different with described the 1st luminescent spectrum; It is characterized in that it is the Sr-Si-N:R base silicon nitride that contains Mn, wherein R is at least a or multiple rare earth element, and wherein Eu is necessary.
14. fluor according to claim 13; It also contains O.
15. according to 14 described fluor of claim the; Wherein based on the total amount of constituent, the content of described O is 3 weight % or lower.
16. it also contains element among at least a or multiple Mg of being selected from, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni fluor according to claim 13.
17. fluor according to claim 13; Wherein based on Sr-Ca, Sr and Ca, the use level of Eu in described fluor is in 0.003 to 0.5mol scope.
18. fluor according to claim 13; Wherein based on Sr-Ca, Sr and Ca, the content of Eu in described fluor is in 0.005 to 0.1mol scope.
19. fluor according to claim 13; Wherein based on Sr-Ca, Sr and Ca, the content of Mn in described fluor is in 0.001 to 0.3mol scope.
20. fluor according to claim 13; Wherein based on Sr-Ca, Sr and Ca, the content of Mn in described fluor is in 0.0025 to 0.03mol scope.
21. fluor according to claim 13; Its median size is 3 μ m or bigger.
22. fluor according to claim 13; Wherein the content of Mn is 5000ppm or lower.
23. a fluor, its absorption has at least a portion of the light of the 1st luminescent spectrum, and sends the light with 2nd luminescent spectrum different with described the 1st luminescent spectrum; It is characterized in that it is the silicon nitride that contains the Ca-Si-N:R base of Mn, wherein R is at least a or multiple rare earth element, and wherein Eu is necessary.
24. fluor according to claim 23; It also contains O.
25. according to 24 described fluor of claim the; Wherein based on the total amount of constituent, the amount of described O is 3 weight % or lower.
26. fluor according to claim 23; It also contains the element among at least a or multiple Mg of being selected from, Sr, Ca, Ba, Zn, B, Al, Cu, Mn, Cr and the Ni.
27. according to claim the 23 described fluor; Wherein based on Sr-Ca, Sr and Ca, the use level of Eu in described fluor is in 0.003 to 0.5mol scope.
28. fluor according to claim 23; Wherein based on Sr-Ca, Sr and Ca, the content of Eu in described fluor is in 0.005 to 0.1mol scope.
29. fluor according to claim 23; Wherein based on Sr-Ca, Sr and Ca, the content of Mn in described fluor is in 0.001 to 0.3mol scope.
30. fluor according to claim 23; Wherein based on Sr-Ca, Sr and Ca, the content of Mn in described fluor is in 0.0025 to 0.03mol scope.
31. fluor, it is selected from first fluor of the silicon nitride of the Sr-Ca-Si-N:R base that contains Mn by two or more, containing second fluor of silicon nitride of Sr-Si-N:R base of Mn and the fluor of the 3rd fluor of silicon nitride that contains the Ca-Si-N:R base of Mn forms, wherein R is one or more rare earth elements, and wherein Eu is necessary.
32. fluor according to claim 23; Its median size is 3 μ m or bigger.
33. fluor according to claim 23; Wherein the content of Mn is 5000ppm or lower.
34 1 kinds of light-emitting devices, it comprises luminous element, it sends the light with the 1st luminescent spectrum; And fluor, it absorbs at least a portion of the light of described the 1st luminescent spectrum, the concurrent light of providing described the 1st luminescent spectrum and the 2nd luminescent spectrum; It is characterized in that it contains fluor according to claim 1.
35. light-emitting device according to claim 34;
Wherein, described fluor comprise be selected from least a by cerium activated yttrium-aluminum oxide fluor, by cerium activated yttrium-gadolinium-aluminum oxide fluor with by cerium activated yttrium-gallium-aluminum oxide fluor.
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