CN1927997A - Fluorescent materials and light emitting device - Google Patents

Fluorescent materials and light emitting device Download PDF

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Publication number
CN1927997A
CN1927997A CNA2006101267617A CN200610126761A CN1927997A CN 1927997 A CN1927997 A CN 1927997A CN A2006101267617 A CNA2006101267617 A CN A2006101267617A CN 200610126761 A CN200610126761 A CN 200610126761A CN 1927997 A CN1927997 A CN 1927997A
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fluor
light
emitting device
wavelength
emission
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高桥向星
广崎尚登
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National Institute for Materials Science
Sharp Corp
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National Institute for Materials Science
Sharp Corp
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Abstract

The present invention provides a JEM phase fluorophor with excellent light efficiency and a light emitting device. The light emitting device comprises a first fluorophor and a second fluorophor, wherein the fluorescence from the second fluorophor is not evidently absorbed by the first fluorophor and the JEM phase fluorophor serves as the first fluorophor. The first fluorophor is a JEM phase fluorophor that does not absorb more than 30% of the fluorescence with the wavelength that has a complementary color relationship with the emitting wavelength of the first fluorophor. In the emitting device having a first fluorophor and a second fluorophor which emits fluorescence having a wave length longer than the fluorescence from the first fluorophor, the first fluorophor does not absorb more than 30% of the fluorescence with the emitting wavelength of the second fluorophor.

Description

Fluor and light-emitting device
Technical field
The present invention relates to a kind of fluor, particularly a kind of oxonitride phosphor and relate to light-emitting device and the semiconductor light-emitting elements that uses this fluor.
Background technology
It is little, low in energy consumption and can stablize the advantage of emission in high brightness ground to have size such as the semiconductor light-emitting apparatus of photodiode (LED).The advantage that provides the light-emitting device of visible light to have semiconductor light-emitting elements by combined semiconductor luminous element and fluor, and also launch desired color according to the purposes of expection, such as white.Therefore, it can be used as telltale, the light switch of the backlight of liquid-crystal display, portable phone or portable information terminal, the display unit that is used for the indoor or outdoors advertisement, various portable equipments, light source of OA (office automation) equipment etc.
Te Kaiping No.10-163535 has disclosed a kind of light-emitting device, and this light-emitting device has made up semiconductor light-emitting elements and one or both fluor of emission indigo plant or royal purple light.Here, select fluor so that by the color of the light of semiconductor light-emitting elements emission and complimentary to one another, thereby therefore launch accurate white light (quasi-white) by the color of the light of fluor emission.
Te Kaiping No.09-153644 has disclosed a kind of dot matrix type display unit, this dot matrix type display unit use the emission peak emission wavelength as the 1II group-III nitride semiconductor of the UV-light of 380nm as excitation light source, and have and launch the trichromatic three kinds of different luminescent coatings of red, green and blue respectively.
In addition, the spy opens flat No.2002-171000 and has disclosed a kind of light-emitting device, and this light-emitting device uses has 390nm to the semiconductor light-emitting elements of 420nm wavelength with by the light activated fluor from described semiconductor light-emitting elements, and the emission white light.Here, semiconductor light-emitting elements emission has the light of low visibility for human eye, and this has obtained so advantage, even when the emissive porwer of semiconductor light-emitting elements or variation in emission wavelength, tone is variation hardly also.In addition, have 390nm and cause hardly for any damage such as the device feature of the resin that has wherein disperseed fluor to the light of 420nm wavelength, and little for the influence of human body.
Routinely, oxide compound or sulfide have been widely used as fluorescent material.Recently, open brochure, the Nato HIROSAKI of flat No.2002-363554 and No.2003-206481, international open WO2005/019376 the spy, Rong-Jun XIE, Koji KIMOTO, Takashi SEKIGUCHI, Yoshinobu YAMAMOTO, Takayuki SUEHIRO, " the Characterization andproperties of green-emitting β-SiAlON:Eu that delivers at Applied Physics Letters 86,211905 (2005) with Mamoru MITOMO 2+Powder phosphors for whitelight-emitting diodes " and Kyota UEDA, Nato HIROSAKI; HajimeYAMAMOTO; and Rong-Jun XIE is at 305th Meeting Technical Digest of PhosphorResearch Society; 2004 has disclosed the example of oxynitride and nitride phosphor in " Red phosphors for warm whitelight-emitting diodes " that pp.37-47 delivers.These fluor are when being launched light by 390nm expeditiously during to the optical excitation of 420nm wavelength, and multiple fluor wherein has outstanding characteristic, change such as high chemical stability, high heat resistance, little luminous efficiency, and both be when use temperature changes.
Te Kaiping No.2004-244560 has disclosed a kind of light-emitting device with following structure.When the luminous element that is excited by the 400nm wavelength excites, fluor (Ca 0.93, Eu 0.05, Mn 0.02) 10(PO 4) 6C 12Have at the peak emission wavelength of royal purple in the blue area, fluor (Ca 0.955Ce 0.045) 2(Si 0.964Al 0.036) 5N 8Have at bluish-green peak emission wavelength in the Green Zone, and fluor SiCaSi 5N 8: Eu has the peak emission wavelength in the red sector at Huang Hong.Caused the light emission the white area from the mixing of the color of these fluor.
In oxonitride phosphor, be known as a kind of silicon oxynitride fluor of the JEM of having phase at the JEM phase fluor disclosed in the brochure of WO2005/019376, and the conventional high-intensity blue light that can not obtain of emission when being excited by near ultraviolet light, JEM is the crystalline phase of a kind of α of being different from SiAlON or β SiAlON mutually.
Te Kaiping No.2004-071357 has disclosed a kind of prior art light-emitting device, this light-emitting device is corresponding to one embodiment of the present of invention, wherein fluor is with the series arrangement of semiconductor light-emitting elements, red fluor, green luminophore and blue fluor, thereby can restrain from the absorption again near the light of the fluor emission of semiconductor element.
In addition, the spy opens flat No.2004-331934 and has disclosed a kind of red fluor La 2O 2S:Eu +Si, it has at least 84%, 94% and 97% powder reflectivity respectively at the red light wavelength of 450nm, 545nm and 624nm or shorter wavelength.
Summary of the invention
First purpose of the present invention is to obtain satisfied luminous efficiency in JEM phase fluor.
Second purpose of the present invention provides a kind of light-emitting device, it has the combination that first fluor and wavelength of light emitted are longer than second fluor of first fluor, wherein the light from the emission of second fluor can significantly not absorbed by first fluor, therefore obtains satisfied luminous efficiency.
Following the device that solves described problem according to the present invention will be described.In order to clarify the reason of using such device why, will some function and the effect relevant with described device be described also.Effect is accessory and is not the basic solution of described problem, and therefore described effect does not limit the scope of the invention.
The invention provides the fluor of the fluorescence of a kind of emission first wavelength, described fluor be longer than first wavelength and with first wavelength be that the wavelength of complementary color relation has 30% photoabsorption at the most, and have JEM mutually as main crystalline phase.With first wavelength be the wavelength that the wavelength of complementary color relation has been represented generation white light when with the light combination of first wavelength.
Preferably, fluor of the present invention is by composition formula M 1-xCe xAl (Siy 1-zAl z) Ny 2-zO zExpression, wherein the M representative is selected from least a element of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x is the real number that satisfies 0.1≤x≤1, y1 is the real number that satisfies 5.9≤y1≤6.1, y2 is the real number that satisfies 10.0≤y2≤10.7, and z satisfies 0.8≤z≤1.2 and the real number of 0.9≤z≤1.1 more preferably.
The contriver has been found that in described fluor, at first wavelength of being longer than fluorescent emission and with first wavelength is that the photoabsorption and the luminous efficiency of wavelength of complementary color relation is relevant, and when with first wavelength be the photoabsorption of wavelength of complementary color relation at the most 30% the time, can obtain good illumination efficiency.
The invention provides a kind of light-emitting device, it comprises: the semiconductor light-emitting elements of launching excitation light; Absorb first fluor of described exciting light and emitting fluorescence; With absorb described exciting light and emission than one type or polytype second fluor by the longer fluorescence of the first fluor emitted fluorescence wavelength, wherein first fluor has 30% photoabsorption at the most (also being called as long wavelength light thereafter absorbs) at the peak emission wavelength by a kind of second fluor emitted fluorescence of main type.
Preferably, according in the light-emitting device of the present invention, the first above-mentioned fluor be longer than first wavelength and with first wavelength be that the wavelength of complementary color relation has 30% photoabsorption at the most, and have JEM mutually as main crystalline phase.
Preferably, in foundation light-emitting device of the present invention, above-mentioned first fluor is by composition formula M 1-xCe xAl (Siy 1-zAl z) Ny 2-zO zExpression, wherein the M representative is selected from least a element of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x is the real number that satisfies 0.1≤x≤1, y1 is the real number that satisfies 5.9≤y1≤6.1, y2 is the real number that satisfies 10.0≤y2≤10.7, and z satisfies 0.8≤z≤1.2 and the real number of 0.9≤z≤1.1 more preferably.
Preferably, in foundation light-emitting device of the present invention, first fluor has 450nm and the peak emission wavelength of 510nm at least at the most.
Preferably, in foundation light-emitting device of the present invention, first fluor has the halfwidth of the emmission spectrum of 80nm at least.
Preferably, according in the light-emitting device of the present invention, has at least 0.05 and at the most 0.25 x tristimulus coordinates and at least 0.02 and 0.38 y tristimulus coordinates at the most from the light of first fluor emission.
Preferably, in foundation light-emitting device of the present invention, a kind of second fluor of main type has 565nm and the peak emission wavelength of 605nm at least at the most.
In foundation light-emitting device of the present invention, for example, when the blue or bluish-green fluorescence of first fluor emission, by the light that uses emission and its complementary colors be the fluor of gold-tinted as second fluor, can obtain to launch the light-emitting device that appears as white light.Here, described a kind of main type refers in the situation of using multiple fluor, is higher than a kind of fluor of other fluor by its fluorescent emission intensity of amount and luminous efficiency decision.
Preferably, in foundation light-emitting device of the present invention, a kind of second fluor of main type has the halfwidth of the emmission spectrum of 80nm at least.
Preferably, in foundation light-emitting device of the present invention, second fluor comprises oxonitride phosphor.
Preferably, in foundation light-emitting device of the present invention, second fluor comprises the α SiAlON fluor that Eu excites.
Preferably, according in the light-emitting device of the present invention, second fluor comprises the α SiAlON fluor that the Eu that contains Li excites.
Preferably, in foundation light-emitting device of the present invention, second fluor comprises by composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-n(1.5≤m≤2.5, n=0.5m) the α SiAlON fluor that excites of Biao Shi Eu.
Preferably, in foundation light-emitting device of the present invention, second fluor comprises the β SiAlON fluor that Eu excites.
Preferably, in foundation light-emitting device of the present invention, second fluor comprises nitride phosphor.
Preferably, in foundation light-emitting device of the present invention, second fluor comprises the CaAlSiN that Eu excites 3
Preferably, according in the light-emitting device of the present invention, semiconductor light-emitting elements, have second member that is dispersed with second fluor and have first member that is dispersed with first fluor and arrange by said sequence.
In foundation light-emitting device of the present invention, second member can also comprise a plurality of members, and the second dissimilar fluor can be dispersed in respectively in a plurality of members.
Preferably, in foundation light-emitting device of the present invention, exciting light has 350nm and the peak emission wavelength of 420nm at least at the most.
Preferably, in foundation light-emitting device of the present invention, the emission of light-emitting device has at least 0.22 and 0.44 x tristimulus coordinates and at least 0.22 and 0.44 y tristimulus coordinates at the most at the most, or the emission of light-emitting device has at least 0.36 and at the most 0.5 x tristimulus coordinates and at least 0.33 and 0.46 y tristimulus coordinates at the most.When light-emitting device of the present invention provides the light emission of above-mentioned tristimulus coordinates, can obtain the light emission of white or incandescent light color, therefore, light-emitting device is specially adapted to illumination.
In the present invention, when the JEM phase fluor that has a low light absorption by the wavelength zone at the wavelength of the fluorescence of being longer than first fluor when first fluor is realized, can obtain good efficiency lf illumination.
In addition, in the present invention, when light-emitting device has emission than second fluor of the long light of ripple of first fluor with when the peak emission wavelength of second fluor has the combination of first fluor of low photoabsorption, the luminous efficiency of first fluor is increased, and can significantly do not absorbed by first fluor from the light of second fluor emission, therefore, can obtain to have on the whole the light-emitting device of outstanding luminous efficiency.
Description of drawings
Fig. 1 has shown the measuring result of the excitation spectrum of the JEM phase fluor described in the preferred embodiment.
Fig. 2 has shown the measuring result of the excitation spectrum of the JEM phase fluor described in the preferred embodiment.
Fig. 3 has shown the measuring result of the excitation spectrum of the JEM phase fluor described in the preferred embodiment.
Fig. 4 has shown the photoabsorption of the JEM phase fluor described in the preferred embodiment and the relation between the luminous efficiency.
Fig. 5 has shown when semiconductor light-emitting elements uses the drive current of 40mA to drive, the relation between the photoabsorption of the JEM phase fluor described in the preferred embodiment and the luminous efficiency of light-emitting device.
Fig. 6 is the sectional view according to the light-emitting device of embodiment 1.
Fig. 7 has shown the emmission spectrum according to the light-emitting device of embodiment 1.
Fig. 8 has shown the emmission spectrum according to the light-emitting device of comparative example 1.
Fig. 9 is the sectional view according to the light-emitting device of embodiment 2.
Figure 10 has shown the emmission spectrum according to the light-emitting device of embodiment 2.
Figure 11 has shown the emmission spectrum according to the light-emitting device of comparative example 3.
Figure 12 has shown the emmission spectrum according to the light-emitting device of embodiment 3.
Figure 13 is the sectional view according to the light-emitting device of embodiment 4.
Figure 14 has shown the emmission spectrum according to the light-emitting device of embodiment 4.
Figure 15 has shown the emmission spectrum according to the light-emitting device of embodiment 5.
Figure 16 is the sectional view according to the light-emitting device of embodiment 6.
Figure 17 is the sectional view according to the light-emitting device of embodiment 7.
Figure 18 has shown by composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-n(m=2.0, n=0.5m) the α SiAlON fluor that excites of Biao Shi Eu excites and emmission spectrum.
Figure 19 has shown the emmission spectrum according to the light-emitting device of embodiment 7.
Figure 20 has shown described in a preferred embodiment by composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-n(m=2.0, n=0.5m) luminous efficiency of the α SiAlON fluor that excites of Biao Shi Eu and the relation of the value in the described composition formula.
Embodiment
The contriver has scrutinized the relation between luminous efficiency and the photoabsorption, finds in JEM phase fluor, when photoabsorption hour can obtain high-luminous-efficiency.This possible reason is when photoabsorption hour the ratio of JEM phase is big and ratio glassy phase is little.
In addition, the contriver has been found that for the proper property of fluor when multiple fluor is used for light-emitting device not only outstanding luminous efficiency but also very important for the little photoabsorption of other wavelength is to improve the luminous efficiency of light-emitting device integral body.Routinely, the spy opens flat No.2004-331934 and comprises preferably explanation at the high-reflectivity (having the negative correlation with photoabsorption) of the wavelength shorter than the fluorescence of emission autofluorescence body.Yet, generally speaking, light that fluor specific absorption wavelength of fluorescence is short and emission light, and therefore be apparent that, in the wavelength zone generation photoabsorption shorter than the wavelength of fluorescence.The contriver has been found that, in indigo plant in bluish-green fluor, particularly in JEM phase fluor, when described fluor and the use of other fluor, it is special when described fluor is used as light-emitting device, have for recently from the little optical absorption of the long light of its wavelength of fluorescence, particularly have green for the long wavelength, be actually important to yellow low light absorption to red light.
In addition, the contriver has realized a kind of light-emitting device, it has utilized this light-emitting device and has outstanding light emission characteristic and be suitable for the fluor mutually with the JEM of other fluor or multiple fluor combination, and has outstanding presenting property of color and the white basic color that is suitable for throwing light on (white, daytime is white, incandescent light color etc.) is provided.
For example, in order to use the emission ultraviolet to realize good presenting property of color in as the light-emitting device of emissive source to the semiconductor light-emitting elements of purple light, need be with well-balanced mode radiative fluor on the wide wavelength region of visible light.For this reason, can mix multiple fluor to obtain high presenting property of color.Yet when the type of blended fluor increased, overall emission intensity reduced because of the absorption again of fluorescence.Consider this problem, utilization has the fact of wide emmission spectrum halfwidth from indigo plant to bluish-green JEM phase fluor with outstanding emission characteristic, JEM phase fluor and fluor are made up with mutual complementary wavelength in visible-range, especially, with JEM phase fluor and the combination of yellow fluor, can obtain to have the light-emitting device of very high presenting property of color and emission natural light thus.In addition, by mixing other fluor, can realize the light-emitting device of higher presenting property of color.
Below, description is absorbed ultraviolet arrive the light of purple and launch blue embodiment and other fluor that arrive the JEM phase fluor of bluish-green light, and will describe the embodiment of use indigo plant to the light-emitting device of the emission Bai Jiguang of the combination of other fluor of bluish-green fluor and visible emitting.
JEM phase fluor
Launch the fluorescence of first wavelength according to fluor of the present invention, and make longer than first wavelength and with first wavelength to have a photoabsorption of wavelength of complementary color relation low.Because lower, so even when this fluor in light-emitting device and other fluor or the use of multiple fluor, also can obtain outstanding luminous efficiency than the photoabsorption of the long wavelength of first ripple.
Longer than first wavelength and with first wavelength be that the photoabsorption of the wavelength of complementary color is set at the most 30%.Then when described fluor was used in the light-emitting device, photoabsorption was enough low, and the luminous efficiency that therefore can obtain.20% photoabsorption is for more preferably at the most, and 15% photoabsorption is further preferred at the most.By find for first wavelength and with the peak emission wavelength of the wavelength of the first wavelength complementary colors, can calculate photoabsorption.
Principal crystalline phase according to fluor of the present invention is the JEM phase.Because principal crystalline phase is the JEM phase, so fluor of the present invention provides the blue bluish-green gratifying fluorescence that arrives.In addition, JEM phase fluor has wide emmission spectrum halfwidth, and when making up with other fluor, particularly with provide with from JEM mutually the fluor wavelength of light emitted be that the fluor combination of the fluorescence of complementary color is advantageous when being used for light-emitting device because can obtain very high presenting property of color and natural light emission.Particularly, only only just can obtain white light in order to compensate from another fluor that departs from of white light by using.
Principal crystalline phase is that JEM means that mutually JEM has occupied 50% or more in the crystalline phase of fluor.For example, from measure the strength ratio of the diffraction peak that obtains by X-ray diffraction, can calculate this ratio.
In the present invention, the wavelength that has with the complementary color of first wavelength relation means the wavelength that white light is provided when the light with first wavelength makes up.Here, " white light " refers to its tristimulus coordinates x is at least 0.22 and at the most 0.44, and tristimulus coordinates y is at least 0.22 and at the most 0.44 light.Therefore, the wavelength that has obtained to have complementary color relation with first wavelength is as the certain wavelengths scope, and in the present invention, and the photoabsorption by this wavelength region is set at the most 30%.
In the present embodiment, JEM is defined as having the material that specific atoms as shown in table 1 plants oneself (atomic arrangement structure) and has the crystalline structure (Pbcn spacer) that is characterized by its coordinate mutually.At Journal of Materials Chemistry Vol.5, November 1995, " the Preparation and Crystal Structure of LaAl (Si that pp2001-2006 delivers at Jekabs Grins etc. 6-zAl z) N 10-zO z" in the details of JEM phase has also been described.
Table 1
Atom The position Coordinate (x) Coordinate (y) Coordinate (z)
(1) RE 8d 0.0553 0.0961 0.1824
(2) Al 4c 0 0.427 0.25
(3) M(1) 8d 0.434 0.185 0.057
(4) M(2) 8d 0.27 0.082 0.52
(5) M(3) 8d 0.293 0.333 0.337
(6) X(1) 8d 0.344 0.32 0.14
(7) X(2) 8d 0.383 0.21 0.438
(8) X(3) 8d 0.34 0.485 0.41
(9) X(4) 8d 0.11 0.314 0.363
(10) X(5) 8d 0.119 0.523 0.127
Spacer: Pbcn
In table 1, the symmetry of spacer has been represented in the indication of " position ".Coordinate x, y and z have represented the positions of elements in corresponding lattice, and get 0 to 1 value.For " atom " row, in cell " RE ", M (being selected from least a element of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) and Ce are placed into possible separately proportion of composing (1-x and x); In " Al ", only put into Al; Arrive in " M (3) " in " M (1) ", Si and Al put into possible separately proportion of composing (6-z and z); Arrive in " X (5) " in " X (1) ", N and O are placed into possible separately proportion of composing (10-z and z).X-ray diffraction by relatively using X ray diffracting data that table 1 calculates and measurement by real material to obtain can determine whether that the material that is obtained has the JEM phase.
Preferably, foundation fluor of the present invention is by composition formula M 1-xCe xAl (Siy 1-zAl z) Ny 2-zO zRepresentative.Here, the M representative is selected from least a element among La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu, x is the real number that satisfies 0.1≤x≤1, y1 is the real number that satisfies 5.9≤y1≤6.1, y2 is the real number that satisfies 10.0≤y2≤10.7, and z satisfies 0.8≤z≤1.2 and the real number of 0.9≤z≤1.1 more preferably.
The advantage of the foundation fluor of being represented by above-mentioned composition formula of the present invention is the high-content that it has the JEM phase and therefore has high-luminous-efficiency.
In above-mentioned composition formula, along with the value x that represents Ce activation amount increases, it is higher that emissive porwer is tending towards, and consider high emission intensity, and the suitable value of x is at least 0.1 and at the most 1.
In above-mentioned composition formula, in ideal JEM phase, expectation y1 and y2 get about 6 and about 10 respectively.Yet, in fact, mixed glassy phase or other crystalline phases, and thus, preferably y1 is at least 5.9 and at the most 6.1, and y2 is at least 10.0 and at the most 10.7.
In above-mentioned composition formula, when the z value is at least 0.8 and at the most 1.2 and when being preferably at least 0.9 and at the most 1.1, JEM phase relatively easily, and therefore such scope is advantageous.
The invention still further relates to a kind of light-emitting device, comprising: the semiconductor light-emitting elements of launching excitation light; Absorb first fluor of described exciting light and emitting fluorescence; With absorb described exciting light and emission than one type or polytype second fluor by the longer fluorescence of the first fluor emitted fluorescence wavelength; Wherein first fluor has 30% photoabsorption at the most at the peak emission wavelength by a kind of second fluor emitted fluorescence of main type.
In light-emitting device of the present invention, first fluor and second fluor are used in combination, and first fluor is suppressed lowly for the photoabsorption by the second fluor emitted fluorescence.Therefore, can obtain to have the light-emitting device of outstanding luminous efficiency.When photoabsorption at the most 30% the time, can obtain the required enough luminous efficiencies of light-emitting device.
In light-emitting device of the present invention, preferably, the first above-mentioned fluor is to have the fluor of JEM as principal crystalline phase, and by such fluor, the light-emitting device that can obtain to have outstanding especially luminous efficiency.
In addition, preferably, first fluor is launched the fluorescence of first wavelength, longer than first wavelength and with first wavelength be that the wavelength of complementary color relation has 30% photoabsorption at the most, and have JEM as its principal crystalline phase.In this situation, when emission is used as second fluor with the fluor that by the wavelength of the first fluor emitted fluorescence is the fluorescence of complementary color relation, can obtain the white-light emitting device of outstanding luminous efficiency, and in addition, by suitably designing the combination of first and second fluor, can also obtain to launch the light-emitting device of the light of incandescent light color with high-luminous-efficiency.
Preferably, in light-emitting device of the present invention, the composition of first fluor is by composition formula M 1-xCe xAl (Siy 1-zAl z) Ny 2-zO zRepresentative, wherein, the M representative is selected from least a element among La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu, x is the real number that satisfies 0.1≤x≤1, y1 is the real number that satisfies 5.9≤y1≤6.1, y2 is the real number that satisfies 10.0≤y2≤10.7, and z satisfies 0.8≤z≤1.2 and the real number of 0.9≤z≤1.1 more preferably.Adopt such fluor, can obtain the light-emitting device of higher photoluminescence efficiency.
Preferably, the peak emission wavelength of first fluor is 450nm and 510nm at least at the most.Promptly first fluor is launched indigo plant satisfactorily to bluish-green light, and the light-emitting device that can obtain to have good luminous efficiency.
In addition, preferably, the halfwidth of the emmission spectrum of first fluor is 80nm at least.In this situation, because the halfwidth of the emmission spectrum of first fluor is wide, so working as is the fluor of the relation of complementary wavelength in visible-range, when the fluor of particularly launching complementary coloured light is used as the combination of first fluor and second fluor, can obtain to have the light-emitting device of the more natural light of presenting property of higher color and emission.
In first fluor, preferably, the light of emission has at least 0.05 and 0.25 x tristimulus coordinates and at least 0.02 and 0.38 y tristimulus coordinates at the most at the most.Then, first fluor is launched blue to bluish-green light satisfactorily.
As first fluor that in light-emitting device of the present invention, uses, promptly blue to bluish-green fluor, preferably use oxonitride phosphor (especially, being launching centre), particularly by composition formula M with silicon, aluminium, oxygen, nitrogen and group of the lanthanides base rare earth element 1-xCe xAl (Si 6-zAl z) N 10-zO zThe Ce of expression 3+Activated JEM phase fluor.
By to have the research of the JEM phase fluor of outstanding emission characteristic to bluish-green district in indigo plant, the contriver has been found that when x value (Ce activated amount) changes in each of the above-mentioned composition formula of JEM phase fluor, the fluor that can obtain, this fluor has peak emission wavelength, wide emmission spectrum halfwidth and high luminous efficiency in indigo plant to bluish-green district.
Fig. 1 has shown when the x value of composition formula changes by composition formula M 1-xCe xAl (Si 6-zAl z) N 10-zO zThe excitation spectrum (that is, intensity of fluorescence is with the wavelength change of exciting light) of the JEM phase fluor of expression.For example, as can be seen, when the x of composition formula value was 0.5, excitation spectrum intensity uprised near 380nm.Reason to this may be by the Ce as launching centre 3+Ionic is absorbed in this wavelength zone and strengthens.Fig. 2 has shown when the x of composition formula value changes by composition formula M 1-xCe xAl (Siy 1-zAl z) Ny 2-zO zThe measuring result of the emmission spectrum of the JEM phase fluor of expression.Here, the light with wavelength of 405nm is used as exciting light.The contriver has been found that by research peak emission wavelength is changing to bluish-green wavelength zone from indigo plant by increasing the x value in the composition formula.Particularly, when in the above-mentioned composition formula during x=1, emission peak wavelength is that the halfwidth of 505nm and emmission spectrum is about 120nm.Because the non-constant width of the halfwidth of emmission spectrum, so yellow component (565nm is to the wavelength of 600nm) and red component (wavelength of 600nm at least) have also been comprised.Therefore, by using another fluor that only is used to adjust from the skew of white, promptly can obtain white light.
Along with the x value in the composition formula is that Ce activated amount increases and the emission reinforcement.Therefore, the preferred value of x is at least 0.1 and at the most 1.0.In addition, from aforementioned, can know La that the proportion of composing with 1-x comprises almost to not contribution of emission, and can usually replace La with the group of the lanthanides primitive, particularly, lanthanon is at least a element that is selected from La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
An embodiment as JEM phase fluor can preferably use than blue fluor as shown in table 2.
In (d), the atomic percent of La and the atomic percent of Ce are 2.75%, and the total atom concentration of these elements is 5.5% at the blue fluor (a) shown in the table 2.In this composition formula, x=0.5.In addition, the stable z value that forms the composition condition of JEM phase fluor of representative permission is z=1.05.When the z value is at least 0.8 and at the most 1.2, can under common creating conditions, obtain the JEM phase, and when the z value at least 0.9 and at the most 1.1 the time, regardless of creating conditions, also can relatively easily obtain the JEM phase.
In the present invention, at above-mentioned composition formula La 1-xCe xAl (Si 6-zAl z) N 10-zO zIn, the x value can be x=1.0, promptly the atomic percent of La can be set at 0%, and the Ce atomic percent can be set at 5.5%.Perhaps, consider stably to form the JEM phase that the z value can be set to z=0.95 in composition formula.
For example, the blue fluor (a) that can make in the following manner in the table 2 arrives (d).Have the oxygen level of average crystal grain diameter, 0.93 quality % of 0.5 μ m and the alpha-silicon nitride powders of 92% α type content, and aluminium nitride powder, lanthanum oxide powder and ceria oxide powder are weighed and are mixed ratio (quality %) to obtain 48.374%, 16.96%, 16.83% and 17.8% respectively.The blended powder is placed in the crucible of boron nitride, and crucible is incorporated in the graphite resistance hot type electric furnace.
Electric furnace is by the vacuum pump exhaust, and is heated to 800 ℃ from room temperature.Here, the nitrogen of 99.999 volume % purity is introduced into and air pressure is set to 1MPa.Then, temperature is increased to sintering temperature, and keeps predetermined sintering time to come sintering with about 500 ℃/hour speed.After sintering, temperature is reduced to room temperature, and fluor is taken out.
Table 2 has shown the mixed powder that uses in the aforesaid way acquisition, and the blue fluor (a) under four kinds of different sintering conditions is to the sintering result of (d).
Here, can determine, when the air pressure of the nitrogen in the electric furnace can obtain JEM phase fluor during for 0.5MPa at least.
Table 2
Sintering temperature Sintering time Photoabsorption (wavelength 400nm) Photoabsorption (wavelength 500nm) Photoabsorption (wavelength 540nm) Photoabsorption (wavelength 590nm) Photoabsorption (wavelength 650nm) The ratio of JEM phase
Blue fluor (a) 1700℃ 30h 0.882 0.18 0.152 0.129 0.108 0.92
Blue fluor (b) 1800℃ 10h 0.814 0.271 0.237 0.208 0.19 0.88
Blue fluor (c) 1700℃ 50h 0.872 0.319 0.295 0.275 0.26 0.81
Blue fluor (c) 1800℃ 30h 0.817 0.37 0.349 0.331 0.314 0.76
By X-ray diffraction and diffraction peak identification, find with the JEM phase ratio in the crystalline phase of above-mentioned mode agglomerating sintered compact, and can determine that JEM occupies at least 50% main ingredient as describing in the international disclosed brochure of WO2005/019376.Unidentified JEM is with respect to the ratio of the whole composition that comprises glassy phase.
Next, (reference: KazuakiOHKUBO etc. are at Journal of the Illuminating Engineering Institute of Japan to use integrating sphere (integrating sphere) to carry out total light flux emission spectroscopy measurements and optical absorption spectra measurement to the fluorophor powder of (d) at blue fluor (a), Vol.83, No.2,1999, " the Absolute Fluorescent Quantum Efficiency ofNBS Phosphor Standard Samples " that pp 87-93 delivers).Be pressed in the reflectivity of thickness by at first using integrating sphere to calculate, calculate photoabsorption by deducting the reflectivity that is calculated then from 1 as the fluorophor powder on the unit of 2mm.
Blue fluor (a) has the peak emission wavelength of 490nm to (d).Fig. 3 shows the wavelength dependency of blue fluor (a) to the photoabsorption of the blue JEM phase fluorophor powder of (d).In each sample, near 400nm and surpass the wavelength of 400nm, photoabsorption significantly reduces.Activated rare earth element in the photoabsorption of the wavelength shorter than 400nm is considered to from JEM phase fluor, and in photoabsorption described in the blue fluor (a) to (d) then from passing through Ce 3+Absorption.At the wavelength of 400nm, every kind of blue fluor (a) to (d) has obtained 80% or more high photoabsorption.On the other hand, arrive in (d) obviously different in the photoabsorption of the wavelength longer at blue fluor (a) than 500nm.
As mentioned above, the peak emission wavelength of blue fluor (a) to (d) is 490nm, and therefore than peak emission wavelength long and with this wavelength be that the wavelength of complementary color relation is in 580 to 600nm scope.
From the result shown in the table 2, as can be seen at blue fluor (a) in (d), fluor (a) to (c) promptly has 30% or lower photoabsorption in the scope at complementary wavelength at 590nm, and blue fluor (d) has at 590nm and is higher than 30% photoabsorption.
The above-mentioned blue fluor (a) that Fig. 4 shows as JEM phase fluor arrives (d) relation between the photoabsorption of the wavelength of 590nm and the luminous efficiency of fluor (=quantum yield * exciting light absorbs).As can be seen, when JEM phase fluor when the wavelength of 590nm has lower photoabsorption, can obtain higher luminous efficiency.For the fluor that has higher luminous efficiency than the fluor of competition mutually is provided, the contriver thinks that at least 0.3 and preferably at least 0.4 luminous efficiency needs.Therefore, be preferably at the most 30%, and more preferably be at the most 20%, and be most preferably at the most 15% in the photoabsorption of the wavelength (Huang) of 590nm.Its reason is as follows.When the content as the JEM phase of crystalline phase reduced, the JEM with high-luminous-efficiency reduced mutually, in addition, glassy phase as amorphous phase increases, because when the fluor crystal that forms the JEM phase by sintering etc., glassy phase is as being by product formation, and this glassy phase has high photoabsorption.
In addition, when photoabsorption in visible-range increases, except the phenomenon that above-mentioned luminous efficiency reduces, a kind of phenomenon has taken place, promptly be absorbed from the light of emission such as the long wavelength's of green, Huang Hehong the fluorescence and the fluor emission that can be used in combination with blue fluor.So the photoabsorption of other wavelength has reduced to use the overall luminous efficiency of the light-emitting device of multiple fluor.Therefore, as can be seen from Figure 5, the luminous intensity of light-emitting device has higher dependency (as described in reference example 1) for photoabsorption, and Fig. 5 has shown the luminous intensity of the light-emitting device the when drive current of the semiconductor light-emitting elements in driving light-emitting device is 40mA and the photoabsorption of fluor.
In addition and since the ratio of the glassy phase in the fluor make batch between change, so photoabsorption batch between also change.As a result, changing appears in the emission balance between JEM phase fluor and other fluor.Therefore, the control of the tone of light-emitting device becomes very difficult.Yet,, can suppress such tonal variation by keeping photoabsorption in predetermined or lower value.
The contriver thinks mainly by suppress to eliminate nitrogen mutually from the JEM as crystalline phase in the sintering process of fluor, and can obtain can a large amount of light absorbing JEM phase fluor at visible-range, promptly have the JEM phase fluor of low glassy phase content.Therefore, as the condition of sintering JEM phase fluor, nitrogen pressure preferably is set at least 0.5MPa and more preferably is 1.0MPa or higher.In order only to improve the crystalline structure of JEM phase, it is long-time to be desirably in high temperature sintering.Yet the contriver has been found that too high or in the time that high temperature keeps when oversize, the ratio of glassy phase increases when temperature.According to noted earlier, sintering temperature desirably is at least 1600 ℃ and 1900 ℃ at the most, and more desirably is at least 1700 ℃ and 1800 ℃ at the most.In addition, sintering time expectation is 50 hours and more desirably be 30 hours at the most at the most.The oxonitride phosphor that obtains by sintering whether finally have JEM mutually or glassy phase be not subjected to (particularly as the rare earth element that activates body, the rare earth element amount is little and be positioned at identical crystallographic site) remarkably influenced, therefore, create conditions and generally speaking can be applicable to have JEM phase fluor such as the not coactivation amount of La or Ce rare earth element.
Notice, at the composition formula M of JEM phase fluor 1-xCe xAl (Siy 1-zAl z) Ny 2-zO zIn, ideal JEM mutually in, expection y1 and y2 are respectively y1=6 and y2=10.Yet in fact, glassy phase or other crystalline phases may be mixed, and therefore the result of compositional analysis has from some deviations of the value of expectation.For example, y1 is about 5.9 to about 6.1, and y2 is about 10.0 to about 10.7.
Second fluor
In light-emitting device of the present invention, second fluor as being used in combination with first fluor can use yellow fluor, red fluor, green luminophore etc.Though second fluor can comprise the fluor of a type or number of different types, but relate to a kind of fluor of main type, make the fluor of winning have 30% photoabsorption at the most at emission peak wavelength by described a kind of main type institute emitted fluorescence.
Preferably, the peak emission wavelength of a kind of main type of second fluor is 565nm and 605nm at least at the most.So, second fluor is launched yellow fluorescence, and when being used in combination with blue first fluor to bluish-green fluorescence of emission, can obtain white light emission.
Preferably, the halfwidth of the emmission spectrum of second fluor of this a kind of main type is 80nm at least.Because the halfwidth of wide emmission spectrum, so the presenting property of color that can obtain.
Preferably, second fluor comprises oxonitride phosphor.Use oxonitride phosphor, can obtain to have the fluor of the halfwidth of the peak emission wavelength of expectation and wide emmission spectrum.
For example, as second fluor of the present invention, the α SiAlON fluor that preferably uses a kind of Eu of comprising to excite.The α SiAlON fluor that this Eu excites is particularly suitable for as the yellow fluor with high emission intensity and wide emmission spectrum halfwidth.
Particularly, preferably include α SiAlON fluor that the Eu of Li excites as yellow fluor with high emission intensity and wide emmission spectrum halfwidth.
Typically, the preferred use comprises by composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-n(1.5≤m≤2.5, n=0.5m) the α SiAlON fluor that excites of Biao Shi a kind of Eu.
When second fluor of the present invention comprises oxonitride phosphor, the β SiAlON fluor that can preferably use a kind of Eu to excite.Emissive porwer that the β SiAlON fluor that Eu excites can provide as green luminophore and wide emmission spectrum halfwidth.
Preferably, second fluor of the present invention comprises nitride phosphor.Emissive porwer that nitride phosphor can provide as red fluor and wide emmission spectrum halfwidth.For example, the CaAlSiN that excites of preferred a kind of Eu of comprising 3Fluor because it has high emissive porwer and wide emmission spectrum halfwidth.
The specific embodiment of Huang as second fluor, red and green luminophore below will be described.
Yellow fluor
As yellow fluor, preferably use by composition formula Ca 0.93Eu 0.07Si 9Al 3ON 15The expression α SiAlON fluor, by composition formula (Ca 0.93Eu 0.07) 0.25Si 11.25Al 0.75ON 15.75The expression α SiAlON fluor or by Li 0.87mSi 12-m-nAl M+nO nN 16-n(m=2.0, n=0.5m) the α SiAlON fluor that excites of Biao Shi Eu is as oxynitride phosphor (particularly, a kind of silicon, aluminium, oxygen, nitrogen and group of the lanthanides base rare earth element that comprises as launching centre).
By composition formula Ca 0.93Eu 0.07Si 9Al 3ON 15The α SiAlON fluor of expression has the halfwidth of the peak emission wavelength of 590nm and the wide 90nm of reaching or wideer emmission spectrum.By composition formula (Ca 0.93Eu 0.07) 0.25Si 11.25Al 0.75ON 15.75The α SiAlON fluor of expression has the halfwidth of the emmission spectrum of the peak emission wavelength of 580nm and about 90nm.By composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-n(m=2.0, n=0.5m) the α SiAlON fluor that excites of Biao Shi Eu has the halfwidth of 573 to 577nm short peak emission wavelength and the wide 90nm of reaching or wideer emmission spectrum.
As shown in figure 20, known to composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-nThe yellow fluor that excites of Eu of expression o'clock has high luminous efficiency in 1.5≤m≤2.5, therefore, can use by composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-n(1.5≤m≤2.5, n=0.5m) Biao Shi fluor.In addition, in order to cover wideer yellow wavelength region, can use described fluor with have by composition formula Ca 0.93Eu 0.07Si 9Al 3ON 15The composition of expression or the mixture or the mixed crystal of similar composition.
The excitation spectrum of above-mentioned fluor all has high peak value in ultraviolet to purple exciting light district.
Produce by composition formula Ca in following mode 0.93Eu 0.07Si 9Al 3ON 15The expression α SiAlON fluor or by composition formula (Ca 0.93Eu 0.07) 0.25Si 11.25Al 0.75ON 15.75The α SiAlON fluor of expression.With silicon nitride, aluminium nitride, lime carbonate and europium sesquioxide powder mixes, put it in the crucible of boron nitride, in having the nitrogen of 1MPa, after 1800 ℃ are reacted 10 hours down, gains are ground.So, produced the α SiAlON fluor that Eu excites.
In the present invention, as second fluor, red fluor can be individually or is used in combination with above-mentioned yellow fluor.As red fluor, preferably use a kind of about 610 fluor that have, and when arriving first combination of phosphors of bluish-green fluorescence, can obtain white light emission with emission indigo plant to the peak emission wavelength of about 670nm.
Red fluor
As red fluor, can use 305 ThMeeting Technical Digest of PhosphorResearch Society, 2004, the CaAlSiN that describes among " the Red phosphors for warm whitelight-emitting diodes " that delivers in the pp.37-47 meeting 3: Eu 3+(Eu activation amount 0.8%) is as nitride phosphor (particularly, a kind of silicon, aluminium, oxygen, nitrogen and group of the lanthanides base rare earth element that comprises as launching centre).Described fluor is produced in following mode.In with respect to the glove box of air and moisture seal,, put it into then in the crucible of boron nitride, in having the nitrogen of 1MPa, after 1800 ℃ are reacted 10 hours down, gains are ground silicon nitride, aluminium nitride, lime carbonate and europium sesquioxide powder mixes.So, produced the CaAlSiN that the Eu of red-emitting excites 3
Above-mentioned by CaAlSiN 3: Eu 3+The red fluor that forms has the halfwidth of the peak emission wavelength of about 650nm and the wide 90nm of reaching or wideer emmission spectrum.
Green luminophore
In light-emitting device of the present invention, green luminophore also can use preferably as second fluor.Green luminophore should preferably be used in combination with yellow fluor and/or red fluor.By such combination, can launch more light near natural light.The preferred peak emission wavelength of green luminophore is 510nm and 565nm at least at the most, and preferred wavelength is 520nm and 550nm at least at the most.
As green luminophore, can use " Characterization and properties of green-emitting β-SiAlON:Eu as delivering at Applied Physics Letters 86,211905 (2005) 2+Powder phosphors for white light-emitting diodes " in the β SiAlON that excites of the Eu that describes as oxygen nitrogen fluor (particularly, a kind of silicon, aluminium, oxygen, nitrogen and group of the lanthanides base rare earth element that comprises as launching centre).This produces in following mode.With silicon nitride, aluminium nitride and europium sesquioxide powder mixes, put it in the crucible of boron nitride, in having the nitrogen of 1MPa, after 1900 ℃ are reacted down, gains are ground.So, produced the β SiAlON fluor that Eu excites.
The green luminophore emission of the β SiAlON that this Eu excites has the high-intensity light of the peak emission wavelength of about 540nm, and it is by the excitation of ultraviolet to purple.The halfwidth of the emmission spectrum of fluor is about 55nm.
Light-emitting device
To describe according to light-emitting device of the present invention with reference to the sectional view of the light-emitting device 60 of embodiment shown in Figure 61.
Light-emitting device 60 comprises substrate 65, be formed at the lip- deep electrode 66 and 67 of substrate 65, be electrically connected to electrode 66 and 67 semiconductor light-emitting elements 64, sealing semiconductor luminous element 64 silicone resin 69, be dispersed in the cast scope of blue fluor 11 in the silicone resin 69 and yellow fluor 20, restriction silicone resin 69 and have the minute surface precision machined surface that contacts with silicone resin 69 to be used for taking out efficiently the framework 68 of light.Electrode 66 and 67 three-dimensionally is guided to as the lower surface that the surface is installed from the upper surface of substrate 65.In light-emitting device 60, blue fluor 11 forms first fluor of the present invention, and yellow fluor 20 forms second fluor of the present invention.
In addition, by changing the proportion of composing of material, the emission peak wavelength of the JEM phase fluor that is used as first fluor of the present invention and can keep high luminous efficiency simultaneously in wide scope Be Controlled as the emission peak wavelength of the Eu activated α SiAlON of second fluor.Utilize this characteristic, can be by not only adjusting the blending ratio of fluor, and the proportion of composing of adjustment fluor, the light-emitting device that has various white tones with design freely, these white color comprise the incandescent light color from the daylight of high colour temperature to low colour temperature, particularly, emission have at least 0.22 and at the most 0.44 x tristimulus coordinates and at least 0.22 and at the most 0.44 y tristimulus coordinates white light and have at least 0.36 and at the most 0.5 x tristimulus coordinates and the light-emitting device of the incandescent light color of at least 0.33 and at the most 0.46 y tristimulus coordinates.
When being used as blue fluor 11 for the blue fluor (a) shown in the table 2 of JEM phase fluor, peak emission wavelength is about 490nm, and the halfwidth of emmission spectrum is wide reaches about 120nm.Therefore, JEM phase fluor has in the light-emitting device of outstanding presenting property of color very useful in manufacturing.Routinely, using ultraviolet in the light-emitting device of purple exciting light, conventional way is the fluor combination with blue, green and red (spy opens flat No.2002-171000).This reason is, though conventional blue fluor has high relatively luminous efficiency, its peak emission wavelength is about 450nm and shorter relatively, and the halfwidth of emmission spectrum is also narrow.
When the above-mentioned blue fluor (a) as JEM phase fluor was used as blue fluor 11, peak emission wavelength was about 490nm, and the halfwidth of emmission spectrum is wide reaches about 120nm, therefore, only by this fluor, visible-range that just can covering wide.In addition, only be combined as the yellow fluor 20 of blue complementary color simply, obtain white light, can realize having the device that emits white light of outstanding presenting property of color.Here, as yellow fluor 20, expect a kind of fluor with 565nm to the peak emission wavelength of 605nm, with by obtaining white light with the combination of blue fluor, and the halfwidth of expecting to have wide 80nm of reaching or wideer emmission spectrum is to improve presenting property of color.In addition, expect yellow fluor by with for the identical exciting light of blue fluor, promptly ultraviolet is to purple exciting light, with high-level efficiency emission light.
Except the above-mentioned light-emitting device of the combination that comprises blue and yellow fluor,, can obtain white light emission by in silicone resin, suitably making up and seal indigo plant, royal purple, Huang, red and green fluor.For example, Fig. 9 of the sectional view of the light-emitting device of reference demonstration embodiment 2 by making up blue fluor 11, yellow fluor 21 and red fluor 30, can obtain white light emission, will illustrate below for embodiment 2.Here, blue fluor 11 forms first fluor, and yellow fluor 21 and blue fluor 30 form second fluor of the present invention respectively.
According in the light-emitting device of the present invention, semiconductor light-emitting elements, first member that has second member of dispersive second fluor and have dispersive first fluor are therein therein arranged by said sequence.
Particularly, light-emitting device can have the structure of light-emitting device 70, and wherein, the layer that has the resin component element of dispersive fluor therein is separated by fluor, shown in the sectional view of Figure 16 of the light-emitting device of foundation embodiment 6.
Light-emitting device 70 comprises substrate 65, be formed at the lip- deep electrode 66 and 67 of substrate 65, be electrically connected to the above-mentioned semiconductor light-emitting elements 64 of electrode 66 and 67, long wavelength's fluorescent donor moiety 71 of sealing semiconductor luminous element 64 (by silicone resin 69A and be dispersed in yellow fluor 20 (α SiAlON fluor) among the silicone resin 69A forms), form the blue fluorescent donor moiety 72 cover long wavelength's fluorescent donor moiety 71 (forming) by silicone resin 69B and blue fluor 11 (JEM is fluor mutually) in being dispersed in silicone resin 69B, the minute surface precision machined surface that the cast scope of restriction silicone resin 69A and 69B and having contacts with silicone resin is to be used for taking out efficiently the framework 68 of light.Here, long wavelength's fluorescent donor moiety 71 and blue fluorescent donor moiety 72 form second member of the present invention and first member respectively.
Though in the embodiment of Figure 16, in long wavelength's fluorescent donor moiety 71, disperseed yellow fluor 20, can disperse to launch than the blue light redder fluor or the green luminophore of long wavelength's color.Perhaps, can disperse in combination that other are green, yellow and red fluor one or more.
In the present invention, second member can also comprise a plurality of members, and in each of this a plurality of members, can disperse the second dissimilar fluor.Particularly, blue fluorescent donor moiety 72 and long wavelength's fluorescent donor moiety 71 can not be two-layer, and long wavelength's fluorescent donor moiety 71 can be divided into multilayer, can disperse different fluorescent materials in these multilayers.For example, long wavelength's fluorescent donor moiety 71 can be divided into two-layerly, more the layer near semiconductor light-emitting elements 64 can be included in the wherein red fluor of dispersive, and another layer then can be included in wherein the yellow fluor of dispersive.Perhaps, long wavelength's fluorescent donor moiety 71 can be divided into three layers, the layer near semiconductor light-emitting elements 64 can be included in the wherein red fluor of dispersive, and the second approaching layer can be included in the wherein yellow fluor of dispersive, and layer farthest then can be included in wherein dispersive green luminophore.
Semiconductor light-emitting elements
With reference to embodiment shown in Figure 6, as the required semiconductor light-emitting elements 64 of light-emitting device 60, can use (typically by the GaN base semiconductor, at least the LED that forms and have the active coating of the InGaN material semi-conductor that comprises Ga and N, and use Al, In and p type doping agent or n type doping agent on demand).
For the emission wavelength of the exciting light of semiconductor light-emitting apparatus, expectation covers the emission peak wavelength of 350nm at least of peak wavelength of the excitation spectrum of JEM phase fluor.Particularly, expect 390nm and the emission peak wavelength of 420nm at least at the most, this emission peak wavelength has obtained satisfied electricity/light conversion efficiency in being used as the InGaN semiconductor light-emitting elements of semiconductor light-emitting elements.In the embodiment of the following stated, having at least, the LED of the emission peak wavelength of 405nm is used as semiconductor light-emitting elements.In addition, in the present invention, can use the semiconductor light-emitting elements that on a surface, has p type electrode and n type electrode.
Embodiment
In following embodiment, used following measuring method.
The halfwidth of emission peak wavelength, emmission spectrum and excitation spectrum
Use integrating sphere, (reference: Kazuaki OHKUBO etc. are at Journal of the Illuminating EngineeringInstitute of Japan to have measured the total light flux emmission spectrum of fluorophor powder and optical absorption spectra, Vol.83, No.2,1999, " the Absolute FluorescentQuantum Efficiency of NBS Phosphor Standard Samples " that pp 87-93 delivers).For this measurement, used F4500 type spectrophotometer (making) by HITACHI.By at first using integrating sphere to calculate to be pressed in thickness as the reflectivity of the fluorophor powder on the unit of 2mm and calculate photoabsorption by deducting the reflectivity that is calculated then from 1.
Fluor colourity changes
Use spectral measurement equipment MCPD700 (making) by Otsuka Electronics Co.Ltd., the tristimulus coordinates of measurement, and estimated from 0 ℃ to 100 ℃ colourity and change.
Embodiment 1
Next, the light-emitting device 60 of embodiment 1 will be described with reference to the sectional view of figure 6.
Light-emitting device 60 comprises substrate 65, be formed at substrate 65 lip- deep electrodes 66 and 67, be electrically connected to electrode 66 and 67 semiconductor light-emitting elements 64, sealing semiconductor luminous element 64 silicone resin 69, be dispersed in the cast scope of blue fluor 11 in the silicone resin 69 and yellow fluor 20, restriction silicone resin 69 and have the minute surface precision machined surface that contacts with silicone resin 69 to be used for taking out efficiently the framework 68 of light.Electrode 66 and 67 three-dimensionally is guided to as the lower surface that the surface is installed from the upper surface of substrate 65.Here, blue fluor 11 forms first fluor of the present invention, and yellow fluor 20 forms second fluor of the present invention.
As blue fluor 11, used above-mentioned blue fluor (a), and, used by composition formula Ca as yellow fluor 20 0.93Eu 0.07Si 9Al 3ON 15The α SiAlON of expression.In order to make light-emitting device emission white light, in silicone resin 69, described two kinds of fluor have been disperseed with 20: 6 ratio of mixture (mass ratio).
Have for a short time as the blue fluor 11 of JEM phase fluor at the wavelength (Huang) of 590nm, therefore, significantly do not absorbed from yellow fluor 20 emitted fluorescence of combination, and blue fluor 11 self has high luminous efficiency to 0.129 photoabsorption.As a result, as shown in Figure 5, when driving semiconductor light-emitting elements 64 with the drive current of 40mA, light-emitting device has obtained the luminous intensity that 1820 millis may (milli candela).
The contriver has studied various fluor, and the Eu activated α SiAlON fluor that discovery is used has in the present embodiment satisfied required condition and has been suitable fluor.Particularly, in the present embodiment, used by composition formula Ca 0.93Eu 0.07Si 9Al 3ON 15The yellow fluor 20 that the α SiAlON fluor of expression is formed.The characteristic that described fluor has is: emission peak wavelength is the wide 90nm of reaching of halfwidth of about 590nm and emmission spectrum or wideer.In addition, excitation spectrum (distribution of fluorescence intensity when the wavelength change of exciting light) has high peak value in the near ultraviolet region.
In the present embodiment, blue fluor can significantly not absorb gold-tinted, has outstanding luminous efficiency as the blue fluor self of JEM phase fluor, and has only used two types fluor in addition, the dispersion amount of phosphor particle in resin is little, can obtain high luminous intensity thus.
Fig. 7 has shown the emmission spectrum that uses the light-emitting device of the above-mentioned two kinds of fluor of blended.Showed the white in daytime of the y tristimulus coordinates of x tristimulus coordinates with x=0.32 and y=0.35 by the light of light-emitting device emission.Present sex index (average color-renderingindex) Ra up to 88 as the average color of photoemissive index naturally.
The light-emitting device of present embodiment also has following advantage.The LED of peak emission wavelength with 405nm of low visibility is used as semiconductor light-emitting elements, and the VISIBLE LIGHT EMISSION of coming selfluminous device is only from fluor.Therefore, in the emmission spectrum that is produced by unshapeliness emissive porwer, only there is little variation as the individual difference of a plurality of LED of excitaton source and LED and fluor.As a result, can obtain stable colourity.In addition, in the present embodiment, used fluor with similar each other physical property (such as proportion).Therefore, it is possible disperseing fluor almost evenly in resin.Therefore, between light-emitting device, photoemissive direction changes little, and the variation in the emission color is little.
In addition, blue fluor 11 and yellow fluor 20 are that oxonitride phosphor forms by one type silicon oxynitride, and wherein the variation of the luminous efficiency that causes owing to temperature variation during driving is little.Therefore, change 1/6 to 1/4 of little light emitting devices to the oxide phosphor that uses following comparative example 1 in the colourity from 0 ℃ to 100 ℃ wide actuation temperature scope.
Comparative example 1
As the example of conventional light-emitting device, known a kind of light-emitting device, the YAG:Ce that it has blue photodiode and launches yellow fluorescence by the exciting light of launching from blue photodiode 3+The combination of fluor (spy opens flat No.10-163535).Fig. 8 has shown the emmission spectrum of the light-emitting device of the comparative example 1 with this structure.Here, by the blue light of photodiode emission with from YAG:Ce 3+The gold-tinted of fluor emission is complimentary to one another, and has therefore launched accurate white light.Yet blue light has narrow emmission spectrum halfwidth, so emissive porwer descends near the wavelength near 500nm.As a result, emmission spectrum is different with natural light, and average color to present sex index Ra be 84, it is lower than the value of embodiments of the invention.
Comparative example 2
As a comparative example 2, make a kind of semiconductor light-emitting apparatus, wherein the blue fluor 11 of embodiments of the invention is replaced by above-mentioned blue fluor (d), and blue fluor (d) has high relatively photoabsorption at long wavelength.When semiconductor light-emitting elements 64 drove with the drive current of 40mA, luminous intensity was that 760 millis may (embodiment 1 42%), and the light of being launched has the x tristimulus coordinates of x=0.35 and the y tristimulus coordinates of y=0.36.Possible reason is as follows.Above-mentioned blue fluor (d) is higher than blue fluor (a) in the photoabsorption of yellow wavelength, and therefore yellow fluorescence decay.In addition, the luminous efficiency of blue fluor (d) self is lower than blue fluor (a).Thereby the interaction that influences of these characteristics has reduced luminous intensity, thereby and cancels each other out and cause the variation of colourity.In addition, prepared five samples of light-emitting device, and the colourity in these samples changes than embodiment 1 greatly.
Embodiment 2
Fig. 9 is a sectional view of launching the light-emitting device 60B of more natural light.With those similar parts shown in Figure 6 by identical reference number indication, and fluor difference only.
In silicone resin 69, disperseed three kinds of dissimilar fluor to obtain white light emission.Particularly, as blue fluor 11, used above-mentioned blue fluor (a), the yellow fluor 21 as above-mentioned has used by composition formula (Ca 0.93Eu 0.07) 0.25Si 11.25Al 0.75ON 15.75The α SiAlON fluor of expression as red fluor 30, has added the CaAlSiN that a spot of Eu excites 3, blending ratio is 20: 6: 2.Here, blue fluor 11 forms first fluor, and yellow fluor 21 and red fluor 30 form second fluor of the present invention respectively.
The red fluor 30 of Shi Yonging has very high luminous efficiency in the present embodiment, and therefore the amount that adds is set to about 10% of fluor total amount.Therefore, significantly do not observe the absorption of the scattering of fluorescence or the exciting light by red fluor, and do not find that almost the luminous intensity of light-emitting device reduces.
Red fluor 30 has the halfwidth of the emmission spectrum of about 95nm, and because only do not obtain enough emissions by blue fluor 11 and yellow fluor 21 at red visible-range, so can obtain flat emmission spectrum.Figure 10 shows the emmission spectrum of the light-emitting device with above-mentioned three kinds of blended fluor.Only white by light-emitting device emission has the x tristimulus coordinates of x=0.37 and the y tristimulus coordinates of y=0.39, and its luminous intensity is that 1520 millis may (when semiconductor light-emitting elements 64 drives with the drive current of 40mA).As seen, on the whole wavelength zone of visible light, realized uniform light emission, and presented sex index Ra up to 96 as the average color of photoemissive index naturally from emmission spectrum.In order to obtain high like this presenting property of color, expect that red fluor 30 has wide 80nm of reaching or wideer emmission spectrum halfwidth.Above-mentioned red fluor 30 has the halfwidth of the emmission spectrum of 95nm.
Comparative example 3
As the comparative example of the prior art of using three kinds of dissimilar fluor, by using blue fluor BaMgAl 10O 17: Eu 2+, green luminophore SrAl 2O 4: Eu 2+With red fluor 0.5MgF 23.5MgOGeO 2: Mn 4+Replace blue fluor 11, yellow fluor 21 and the red fluor 30 of embodiment 2, thereby made light-emitting device.The emmission spectrum that is obtained and has been launched the white light in daytime of the y tristimulus coordinates of x tristimulus coordinates with x=0.35 and y=0.37 as shown in Figure 11.As from the emmission spectrum finding, average color presents sex index Ra and is low to moderate 60.The luminous intensity of the light-emitting device of comparative example 3 is that 1120 millis are born (when the drive current that adopts 40mA drives semiconductor light-emitting elements 64).
Embodiment 3
Next, use three types fluor, made the light-emitting device that obtains warmer photoemissive naturally embodiment 3.With reference to figure 9, in this light-emitting device, blue fluor 11 is replaced by bluish-green fluor, by composition formula (Ca 0.93Eu 0.07) 0.25Si 11.25Al 0.75ON 15.75The α SiAlON fluor of expression is used as yellow fluor 21, the CaAlSiN that Eu excites 3Be used as red fluor 30.That is, fluor and blending ratio (mass ratio) have only been changed.
In the present embodiment, in JEM phase fluor, used the bluish-green fluor that does not contain La and contain the Ce of proportion of composing x=1 as first fluor.Peak emission wavelength is about 505nm, and the wide 120nm that reaches of the halfwidth of emmission spectrum, and this is rare in emission indigo plant in other fluor of blue green light.Therefore, to have in the light-emitting device of outstanding presenting property of color in manufacturing be very useful to JEM phase fluor.In addition, the photoabsorption of bluish-green fluor is 21% and is 18% at the wavelength of 650nm at the wavelength of 580nm, and these wavelength are the complementary color relation with wavelength as the 505nm of first wavelength of the present invention.
In addition, as yellow fluor by composition formula (Ca 0.93Eu 0.07) 0.25Si 11.25Al 0.75ON 15.75The α SiAlON fluor of expression has the peak emission wavelength of 580nm and the wide emmission spectrum halfwidth of about 90nm.
In addition, in order to make emmission spectrum more near natural light, the CaAlSiN that Eu is excited 3Adding is as red fluor 30.In order to obtain the light emission of warmer color, it is about 50% to be used to replace the blending ratio (mass ratio) of bluish-green fluor of the blue fluor of embodiment 2 to reduce, and the blending ratio of red fluor (mass ratio) has increased about 25%.Particularly, bluish-green: Huang: the blending ratio between red (mass ratio) is set at 10: 6: 2.5.
Figure 12 has shown the emmission spectrum of the light-emitting device of the mixture that uses three types above-mentioned fluor.Have so-called incandescent light color from the light of this launching device emission, have the x tristimulus coordinates of x=0.43 and the y tristimulus coordinates of y=0.41.From emmission spectrum as can be seen, obtained to have the light of emmission spectrum of light source A of being near the mark very much, and presented sex index Ra up to 94 as the average color of photoemissive index naturally.
In addition, because the red fluor of Shi Yonging has very high luminous efficiency in the present embodiment,, can improve the emissive porwer in red sector territory by increasing addition a little.In addition, because reduced to have the blending ratio (mass ratio) of the low relatively visibility and the blue fluor of relative low luminous efficiency, so the luminous intensity of light-emitting device does not reduce from embodiment 3, although total light has the emmission spectrum of the low incandescent light color of luminous intensity.
Embodiment 4
Next, made the light-emitting device that obtains more natural photoemissive embodiment 4.
Figure 13 is the sectional view of light-emitting device 60C.Here, meet indication with the similar parts of Fig. 6 by identical reference.In the light-emitting device of present embodiment, disperseed four kinds of different fluor to obtain white light emission.Particularly, as blue fluor 11, used above-mentioned blue fluor (a), the yellow fluor 20 as above-mentioned has used by composition formula Ca 0.93Eu 0.07Si 9Al 3ON 15The α SiAlON fluor of expression has added the CaAlSiN that Eu excites 3Fluor is as red fluor 30, and mixed β SiAlON fluor that a spot of Eu excites as green luminophore 40.Blending ratio (mass ratio) is 20: 6: 2: 2.Here, blue fluor 11 is formed first fluor, and yellow fluor 20, red fluor 30 and green luminophore 40 are formed second fluor of the present invention respectively.
Green luminophore 40 is launched high-intensity light, has the wavelength of about 540nm, has ultraviolet to purple exciting light.The halfwidth of the emmission spectrum of fluor is about 55nm.Provide green luminophore 40 to fill gap between blue fluor 11 and the yellow fluor 20, and therefore at least the halfwidth of 45nm be enough.And in the present embodiment, if the halfwidth of green luminophore 40 is too wide, then the Pingdu of emmission spectrum will be lost because shown in wavelength zone have high visibility, caused non-natural light emission.Here, desirably, the emission peak wavelength of green luminophore 40 is 510nm and 565nm at least at the most, and more desirably, 520nm and 550nm at least at the most.
Figure 14 has shown the emmission spectrum of the light-emitting device with above-mentioned four kinds of dissimilar fluor.Photoemissive gap in the Green Zone can be covered by green luminophore, and this gap is caused by the use that use has the blue fluor of the emmission spectrum that is offset slightly with respect to short wavelength side.
Only white from the emission of described light-emitting device has the x tristimulus coordinates of x=0.35 and the y tristimulus coordinates of y=0.37.From described emmission spectrum as can be seen, on the whole wavelength zone of visible light, realized uniform light emission, and presented sex index Ra up to 98 as the average color of photoemissive index naturally.
In addition, the green luminophore of Shi Yonging has very high luminous efficiency and has peak emission wavelength at the wavelength zone of high visibility in the present embodiment, therefore, the amount of its adding be set to fluor total amount about 10%.Therefore, with embodiment 1 and 2 relatively, by the luminous intensity of the light-emitting device that amount caused of the increase of fluor reduce almost do not observe.
Embodiment 5
Next, made the light-emitting device that obtains warmer photoemissive naturally embodiment 5.The section of light-emitting device is identical with embodiment shown in Figure 13 4, except having replaced fluor.
In silicone resin 96, disperseed four kinds of dissimilar fluor to obtain the light emission of incandescent light color.Particularly, disperseed to replace blue fluor 11 bluish-green fluor, as yellow fluor 20 by composition formula (Ca 0.93Eu 0.07) 0.25Si 11.25Al 0.75ON 15.75The α SiAlON fluor of expression, the CaAlSiN that excites as the Eu of red fluor 30 3The green luminophore 40 of the β SiAlON that fluor and Eu excite.
In order to obtain the light emission of warmer color, the blending ratio (mass ratio) of blue (bluish-green) fluor has reduced about 50% from embodiment 4, and the blending ratio of Huang/red fluor (mass ratio) has increased about 10%.Particularly, bluish-green: Huang: red: the blending ratio between green (mass ratio) is set at 10: 6.6: 2.2: 1.6.
Figure 15 has shown the emmission spectrum of the light-emitting device of the light-emitting device with the above-mentioned four kinds of fluor of blended.Incandescent light color from the y tristimulus coordinates of the x tristimulus coordinates that only has x=0.45 of this light-emitting device emission and y=0.42.From emmission spectrum as can be seen, obtained to have the light of emmission spectrum of light source A of being near the mark very much,, and presented sex index Ra up to 94 as the average color of photoemissive index naturally except exciting the light wavelength of low visibility.
In addition, because the red/yellow fluor of Shi Yonging has very high luminous efficiency in the present embodiment, so, can improve the emissive porwer in red/yellow zone by increasing addition a little.In addition, because the blending ratio (mass ratio) that has reduced blue fluor is to obtain the light of incandescent light color, so compare the reduction of almost not observing the luminous intensity of light-emitting device with embodiment 4, although the described ratio that only wherein has the light of low visibility is higher than the incandescent light color of white.
Embodiment 6
Next, will describe light-emitting device 70, and wherein be used to disperse the resin component element of fluor to divide by fluor with reference to the sectional view of Figure 16.
Light-emitting device 70 comprises substrate 65, be formed at substrate 65 lip- deep electrodes 66 and 67, be electrically connected to the above-mentioned semiconductor light-emitting elements 64 of electrode 66 and 67, long wavelength's fluorescent donor moiety 7 of sealing semiconductor luminous element 64 (by silicone resin 69A and be dispersed in yellow fluor 20 (α SiAlON fluor) among the silicone resin 69A forms) 1, form the blue fluorescent donor moiety 72 cover long wavelength's fluorescent donor moiety 71 (forming) by silicone resin 69B and blue fluor 11 (JEM is fluor mutually) in being dispersed in silicone resin 69B, limit the cast scope of silicone resin 69A and 69B and have the framework 68 of minute surface precision machined surface that contacts with silicone resin to take out light efficiently.Here, long wavelength's fluorescent donor moiety 71 and blue fluorescent donor moiety 72 form second member of the present invention and first member respectively.
In the present embodiment, above-mentioned blue fluor (a) is used as blue fluor 11, by composition formula Ca 0.93Eu 0.07Si 9Al 3ON 15The α SiAlON fluor of expression is used as yellow fluor 20.
In this mode, because blue fluorescent donor moiety 72 and long wavelength's fluorescent donor moiety 71 are separated, and long wavelength's fluorescent donor moiety 71 is provided with more near semiconductor light-emitting apparatus 64, and high-intensity gold-tinted is from being arranged on yellow fluor 20 emissions that exciting light has high-intensity part.Yet blue fluorescent donor moiety 72 is arranged at the outside, and therefore, if gold-tinted is absorbed in this part height, gold-tinted will be hindered to the emission of light-emitting device outside, causes the reduction of total luminous intensity.Therefore, when having adopted such structure, bluely compare with the embodiment 1 of yellow fluor with wherein mixing in resin and disperseed, reduction becomes even more important by blue fluor 11 for the photoabsorption of Huang.Mode with present embodiment, be suppressed to predetermined value or lower blue fluor by the photoabsorption of arranging for light with long wavelength, the photoabsorption (inhibition) of synergistic effect that can obtain to arrange (inhibition by yellow fluor) and long wavelength light for the effect of indigo plant to the photoabsorption of blue green light by the effect of blue fluor for the photoabsorption of Huang, thereby can obtain to have the light-emitting device of high luminous efficiency, it has represented the luminous intensity (when using the replacement current drives semiconductor light-emitting elements 64 of 40mA) that 2020 millis are born.
Embodiment 7
Figure 17 is the sectional view of the light-emitting device 60C of emission nature and brighter light.Indicate by identical reference symbol with the parts that Fig. 9 is similar, only the fluor difference.
In silicone resin 69, three kinds of different fluor are disperseed to obtain white light emission.Particularly, indigo plant: Huang: red blending ratio (mass ratio) is set at 20: 6: 2.
As yellow fluor, used by composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-n(m=2.0, n=0.5m) the α SiAlON fluor that excites of Biao Shi Eu.With use among the embodiment 2 by composition formula Ca 0.93Eu 0.07Si 9Al 3ON 15α SiAlON fluor and other peak emission wavelengths of expression are that the embodiment of 590nm compares, and the fluor of present embodiment has 573 to 577 shorter peak emission wavelength.Fluor has the halfwidth of the wide emmission spectrum of 90nm at least.Figure 18 has shown the representational excitation spectrum and the emmission spectrum of fluor.When using yellow fluor 22, the luminous intensity of increase becomes easier, because its peak emission wavelength is near the high visibility district of human eye.
Figure 19 has shown the emmission spectrum of the light-emitting device with three kinds of above-mentioned different fluor of blended.Only white from light-emitting device emission has the x tristimulus coordinates of x=0.36 and the y tristimulus coordinates of y=0.39, and has the luminous intensities that 1720 millis bear (when with the replacement current drives semiconductor light-emitting elements 64 of 40mA).From emmission spectrum as can be seen, on the whole wavelength zone of visible light, realized uniform light emission, and presented sex index Ra up to 94 as the average color of the indication of natural light.Therefore, find that using the yellow fluor of present embodiment is the presenting property of color and the high luminous intensity to realize being satisfied with of expectation.
Other possibilities
Though in an embodiment fluor is dispersed in the silicone resin, resin can such as Resins, epoxy, maybe can use other transparent material, such as glass for different resins.To red fluor, not only can add those fluor described in the embodiment for green luminophore, also can add those fluor of comparative example.In addition, can use fluor or multiple fluor except above-mentioned, such as TAG (TbA L3O 12) fluor.
In addition, though in above embodiment, LED is used as semiconductor light-emitting elements, can use semiconductor laser.In addition, excite light wavelength can be any wavelength, as long as it has realized the electricity/light conversion efficiency of the satisfaction of semiconductor light-emitting elements, and near the peak wavelength of the excitation spectrum of this fluor.
Though described and illustrated the present invention in detail, can be expressly understood above-mentionedly only to be embodiment but not to be used for restriction, only limited in the spirit and scope of the present invention by the clause of claim.
The application is based on Japanese patent application No.2005-258114, the No.2006-000234 and the No.2006-2187836 that submit in Japanese Patent office respectively on September 6th, 2005, on January 4th, 2006 and on August 10th, 2006, and its full content is hereby incorporated by.

Claims (20)

1, the fluor of the fluorescence of a kind of emission first wavelength, described fluor be longer than described first wavelength and with described first wavelength be that the wavelength of complementary color relation has 30% photoabsorption at the most, and have JEM mutually as main crystalline phase.
2, fluor according to claim 1, described fluor is by composition formula M 1-xCe xAl (Si Y1-zAl z) N Y2-zO zExpression,
Wherein the M representative is selected from least a element among La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu,
X is the real number that satisfies 0.1≤x≤1,
Y1 is the real number that satisfies 5.9≤y1≤6.1,
Y2 is the real number that satisfies 10.0≤y2≤10.7, and
Z is the real number that satisfies 0.8≤z≤1.2.
3, a kind of light-emitting device, it comprises:
The semiconductor light-emitting elements of launching excitation light;
Absorb first fluor of described exciting light and emitting fluorescence; With
Absorb described exciting light and emission than one type or polytype second fluor, wherein by the longer fluorescence of the described first fluor emitted fluorescence wavelength
Described first fluor has 30% photoabsorption at the most at the peak emission wavelength by a kind of described second fluor emitted fluorescence of main type.
4, light-emitting device according to claim 3, wherein
Described first fluor is the fluor according to claim 1.
5, light-emitting device according to claim 3, wherein said first fluor has 450nm and the peak emission wavelength of 510nm at least at the most.
6, light-emitting device according to claim 3, wherein said first fluor has the halfwidth of the emmission spectrum of 80nm at least.
7, light-emitting device according to claim 3 wherein has at least 0.05 and at the most 0.25 x tristimulus coordinates and at least 0.02 and 0.38 y tristimulus coordinates at the most from the light of described first fluor emission.
8, light-emitting device according to claim 3, wherein a kind of described second fluor of main type has 565nm and the peak emission wavelength of 605nm at least at the most.
9, light-emitting device according to claim 3, wherein a kind of described second fluor of main type has the halfwidth of the emmission spectrum of 80nm at least.
10, light-emitting device according to claim 3, wherein said second fluor comprises oxonitride phosphor.
11, light-emitting device according to claim 10, wherein said second fluor comprise the α SiAlON fluor that Eu excites.
12, light-emitting device according to claim 11, wherein said second fluor comprise the α SiAlON fluor that the Eu that contains Li excites.
13, light-emitting device according to claim 11, wherein said second fluor comprises by composition formula Li 0.87mSi 12-m-nAl M+nO nN 16-nThe α SiAlON fluor that excites of Eu of expression, 1.5≤m≤2.5 wherein, n=0.5m.
14, light-emitting device according to claim 10, wherein said second fluor comprise the β SiAlON fluor that Eu excites.
15, light-emitting device according to claim 3, wherein said second fluor comprises nitride phosphor.
16, light-emitting device according to claim 15, wherein said second fluor comprises the CaAlSiN that Eu excites 3
17, light-emitting device according to claim 3, has second member that is dispersed with described second fluor and has first member that is dispersed with described first fluor and be arranged in order at wherein said semiconductor light-emitting elements.
18, light-emitting device according to claim 17, wherein said second member also comprises a plurality of members, and dissimilar described second fluor is dispersed in respectively in described a plurality of member.
19, light-emitting device according to claim 3, wherein said exciting light have 350nm and the peak emission wavelength of 420nm at least at the most.
20, light-emitting device according to claim 3, the emission of wherein said light-emitting device has at least 0.22 and 0.44 x tristimulus coordinates and at least 0.22 and 0.44 y tristimulus coordinates at the most at the most, or the emission of described light-emitting device has at least 0.36 and at the most 0.5 x tristimulus coordinates and at least 0.33 and 0.46 y tristimulus coordinates at the most.
CNA2006101267617A 2005-09-06 2006-09-06 Fluorescent materials and light emitting device Pending CN1927997A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP258114/05 2005-09-06
JP2005258114 2005-09-06
JP000234/06 2006-01-04
JP217836/06 2006-08-10

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103676136A (en) * 2012-09-19 2014-03-26 精工爱普生株式会社 Spectroscope, wavelength variable interference filter, optical module, and electronic device
CN105255494A (en) * 2014-07-14 2016-01-20 Lg电子株式会社 Yellow light emitting phosphor and light emitting device package using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103676136A (en) * 2012-09-19 2014-03-26 精工爱普生株式会社 Spectroscope, wavelength variable interference filter, optical module, and electronic device
CN105255494A (en) * 2014-07-14 2016-01-20 Lg电子株式会社 Yellow light emitting phosphor and light emitting device package using the same

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