CN1842673A - Light-emitting device and phosphor - Google Patents
Light-emitting device and phosphor Download PDFInfo
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- CN1842673A CN1842673A CNA2004800246222A CN200480024622A CN1842673A CN 1842673 A CN1842673 A CN 1842673A CN A2004800246222 A CNA2004800246222 A CN A2004800246222A CN 200480024622 A CN200480024622 A CN 200480024622A CN 1842673 A CN1842673 A CN 1842673A
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- light
- illuminator
- emitting device
- phosphor body
- phosphor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Abstract
A light emitting device having a combination of an exciting source producing a 420-500-nm-wavelength light and a phosphor, and a high luminance. The light emitting device comprises a first light emitting element producing a 420-500-nm-wavelength light, and a second light emitting element producing a visible light on receiving a light applied from the first light emitting element, characterized in that the second light emitting element contains a phosphor, and the object color of the phosphor satisfies, in a L*, a*, b* color specification system, L*>=90, -22<=a*<=-10, b*>=55.
Description
Technical field
The present invention relates to a kind of light-emitting device.More particularly, the present invention relates to a kind of light-emitting device and a kind of phosphor body that can produce white light efficiently, described light-emitting device has made up first illuminator and second illuminator that contain the material for transformation of wave length that can absorb this blue light and launch gold-tinted of emission from the blue region light of power supply.
Background technology
Developed at present and can launch from blueness to red visible-range until purple light or ultraviolet light emitting diode (LED) or laser diode (LD).Be used in combination these multi-colored led display unit and can be used for display or traffic signalling device.In addition, also proposed to change the light-emitting device of the glow color of LED or LD with phosphor body.For example, special public clear 49-1221 communique discloses following method: the laser beam that will launch the radiation beam of 300～530nm wavelength is radiated at phosphor material (Ln
3-x-yCe
xGd
yM
5-zGa
zO
12(Ln represents Y, Lu or La, and M represents Al, Al-In or Al-Sc, and x is 0.001～0.15, and y is at the most 2.999, and z is at the most 3.0)) on, make it luminous and demonstrate image.
In addition, in recent years, emission source as image display device or lighting device, proposed the light-emitting device that emits white light, described light-emitting device combines by high gallium nitride (GaN) the type LED of the luminous efficiency of being attracted attention as the blue-light semiconductor radiated element or LD and as the phosphor body of material for transformation of wave length.Te Kaiping 10-190066 communique discloses a kind of emission white light devices, wherein, the blue led or the LD chip that are used in combination phosphor body and make by nitride-type semiconductor, in described phosphor body, replace a part of Y in the yttrium-aluminium-garnet phosphor body of cerium activation with Lu, Sc, Gd or La, thus the gold-tinted colour mixture of blue light and phosphor body emission and form white light.Te Kaiping 10-247750 communique discloses the color conversion profile member that obtains with the yttrium aluminum oxide fluorescent material of cerium activation by combination and LED lamp etc., and the yttrium aluminium oxide fluorescent material of described cerium activation has at least a elemental constituent and/or the Si elemental constituent that is selected from the group of being made up of Ba, Sr, Mg, Ca and Zn.
In addition, the spy opens flat 10-242513 communique and discloses a kind of phosphor body, wherein replaces a part of Y in the yttrium-aluminium-garnet phosphor body of cerium activation with Sm.In addition, special table 2003-505582 or special table 2003-505583 communique disclose the effect that Tb is added to resulting phosphor body in the yttrium-aluminium-garnet phosphor body of cerium activation.
But in the combination of the yttrium-aluminium-garnet phosphor body of above-mentioned disclosed cerium activation and blue led or blue laser, the luminous intensity of white light is still not enough, therefore, needs the efficient of improvement blue led.And for such phosphor body, its luminous intensity is also still not enough, therefore, requires further improvement efficient and realizes energy-saving illumination.
In addition, for temperature characterisitic, when connecting as the LED of first illuminator or LD, the temperature around the chip increases, thereby the efficient of LED or LD reduces, and because this temperature increases, the phosphor body that is contained in second illuminator also will reduce its briliancy greatly.Usually, quality changes with the composition of parent and the type and the quantity of activator, therefore, needs to use luminous intensity height and luminous intensity to reduce little material because of this temperature increases.
For light-decay characteristic, especially give me a little bright display or when backlight when adopting to drive by pulse as the LED of first illuminator or LD, if the persistence of the phosphor body that second illuminator is contained is extremely short, with having flicker and the problem that can not obtain enough picture characteristics, therefore need improve.
Summary of the invention
The problem to be solved in the present invention
The present invention develops a kind of by making yellow phosphor body luminous with blue led or LD, thereby brighter light-emitting device in the white-light emitting system, particularly, the objective of the invention is provides the light-emitting device of high briliancy by developing high efficiency yellow phosphor body, and the present invention also provides the phosphor body of high briliancy.
The method of dealing with problems
The inventor has carried out further investigation and has solved the problems referred to above, the result, in the research of the luminous efficiency that is primarily aimed at the yttrium-aluminium-garnet phosphor body that improves conventional cerium activation, they find, even phosphor body has all identical compositions and identical crystallographic system, object color also has significant change, and when being installed in phosphor body among the LED, between the object color of phosphor body and briliancy, exist strong correlation, therefore, when use has the fluorescent powder of object color of specific tendency, promptly compare with the phosphor body of routine, use L with par
*And a
*But, b
*When exceeding the fluorescent powder of certain value at least, the briliancy of LED will uprise.Finished the present invention according to these discoveries.And, they also find, for the object color that makes the phosphor body powder in specific color gamut, essential conditions such as temperature in the time of can optimizing calcining and atmosphere, thereby can obtain object color than better phosphor body in the past, use the light-emitting device of such phosphor body to have high briliancy, and have high temperature characterisitic or light-decay characteristic.Like this, finished the present invention according to these discoveries.
Promptly, the invention provides a kind of light-emitting device with first illuminator and second illuminator, the light of described first illuminator emission, 420～500nm wavelength, when penetrating described second illuminator with the illumination of described first illuminator, described second illuminator is launched visible light, it is characterized in that described second illuminator contains phosphor body, the object color of this phosphor body satisfies L
*, a
*, b
*L in the colour system
*〉=90 ,-22≤a
*≤-10 and b
*〉=55, and object color satisfies L
*, a
*, b
*L in the colour system
*〉=90 ,-22≤a
*≤-10 and b
*〉=55 phosphor body is characterised in that, it contains the crystalline phase of the chemical composition of (1) expression that has following formula:
(Ln
1-a-bCe
aTb
b)
3M
5O
12Formula (1) wherein, Ln is at least a element that is selected from the group of being made up of Y, Gd, Sc, Lu and La, M is at least a element that is selected from the group of being made up of Al, Ga and In, a and b are respectively the numerical value that satisfies 0.001≤a≤0.3 and 0≤b≤0.5.
Effect of the present invention
Can provide a kind of the have light-emitting device of high briliancy and phosphor body according to the present invention with high briliancy.
Description of drawings
Fig. 1 is the emission spectrum of phosphor body under 465nm excites of embodiment 1.
Fig. 2 is expression contacted or be molded over an embodiment of the light-emitting device on the surface light emitting GaN type diode with the second membranaceous illuminator a schematic diagram.
Fig. 3 is the schematic sectional view of an embodiment of the expression light-emitting device that comprises first illuminator (illuminator of 420～500nm) and second illuminator of the present invention.
Fig. 4 is the schematic sectional view of an embodiment of of the present invention litillumination devices of expression.
Symbol description
1 second illuminator
2 luminous GaN type LD
3 substrates
4 light-emitting devices
5 supports lead-in wire
6 leads
7 first illuminators (illuminator of 420～500nm)
8 contain the resin part of phosphor body of the present invention
9 leads
10 profile members
11 wherein are equipped with the face litillumination devices of light-emitting component
12 shells
13 light-emitting components
14 diffuser plates
The specific embodiment
The invention provides a kind of first illuminator and the light-emitting device that contains second illuminator of phosphor body with light of emission 420～500nm wavelength, the object color of above-mentioned phosphor body satisfies L
*, a
*, b
*L in the colour system
*〉=90 ,-22≤a
*≤-10 and b
*〉=55, thus the luminous intensity of phosphor body uprises, and light-emitting device has high briliancy.Because can not handle by luminous object penetrated by illumination, so L
*Usually be no more than 100, but phosphor body of the present invention can excite by illuminated light source, sends the light overlapping with reverberation, thus L
*Can surpass 100.Therefore, the upper limit is generally L
*≤ 100.And from the angle of high briliancy, a
*Be preferably a
*≤-14, more preferably a
*≤-16.b
*Be preferably b
*〉=65, more preferably b
*〉=68.The invention is characterized in b
*The value height, and b
*Value better when high.Its upper limit is b in theory
*≤ 200, common b
*≤ 120.
There is no particular limitation to the phosphor body that contained in the light-emitting device of the present invention, just passable as long as object color satisfies above-mentioned scope.But, from the stable angle of material, preferably to make as parent with oxide, such oxide more preferably has garnet structure.And preferred described phosphor body contains Ce or Ce and Tb.
Especially, preferred phosphor body contains the crystalline phase that has by the chemical composition of following formula (1) expression:
(Ln
1-a-bCe
aTb
b)
3M
5O
12Formula (1)
In the formula (1), Ln is at least a element that is selected from the group of being made up of Y, Gd, Sc, Lu and La, is preferably at least a element that is selected among Y and the Gd especially.
In the formula (1), M is at least a element that is selected from the group of being made up of Al, Ga and In, is preferably Al especially.
The a of expression Ce mol ratio is the numerical value that satisfies 0.001≤a≤0.3, and still from the angle of high luminous intensity, its lower limit is preferably a 〉=0.01, more preferably a＞0.01, and a 〉=0.02 more preferably, its upper limit is preferably a≤0.2, more preferably a≤0.18, and more preferably a≤0.15.
The b of expression Tb mol ratio is the numerical value that satisfies 0≤b≤0.5, and when Tb is included in the phosphor body, luminous intensity will uprise, and therefore, the lower limit of the scope of b is preferably b 〉=0.01, more preferably b＞0.01, and more preferably b 〉=0.02, preferred especially b＞0.02.
On the other hand, from the angle of temperature characterisitic, if the ratio of Tb increases, temperature characterisitic will reduce, and therefore, the upper limit of the scope of b is preferably b＜0.5, more preferably b≤0.4, and more preferably b≤0.2, preferred especially b≤0.17, most preferably b＜0.17.And with respect to the luminous intensity of the phosphor body under the room temperature, the luminous intensity of phosphor body is kept highly more under heated condition, and temperature characterisitic is just high more.Estimate the temperature characterisitic of employed phosphor body in the light-emitting device of the present invention in the following manner: at 100 ℃ of optical excitation phosphor bodies of using the 465nm wavelength down, measure consequent luminous, obtain the value (luminous intensity) of peak maximum of the emission spectrum of phosphor body like this, will be worth then with value and compare as the peak maximum of the emission spectrum of the phosphor body of measuring similarly under 25 ℃ of standard value.The employed phosphor body of light-emitting device of the present invention is at least 90% of luminous intensity under 25 ℃ usually in the luminous intensity under 100 ℃.
And from the angle of light-decay characteristic, the phosphor body that contains Tb will have good light-decay characteristic, therefore, when the mol ratio b of Tb preferably is adjusted to b 〉=0.02, more preferably b 〉=0.04, and more preferably b 〉=0.1, preferred especially b 〉=0.2 o'clock, light-decay characteristic improves.Here, obtain light-decay characteristic in the following manner: excite phosphor body, obtain exciting the luminous intensity of twilight sunset after stopping to become then exciting 1/10 the time (t1) of luminous intensity of moment before stopping and the luminous intensity of twilight sunset to become for 1/100 time (t2).T1 ratio long more or t2/t1 is big more, and light-decay characteristic is high more.The t1 of the employed phosphor body of light-emitting device of the present invention is generally 15ns (nanosecond) at least, preferred 160ns at least, more preferably 170ns at least, and more preferably 190ns at least, there is no particular limitation to its upper limit, but be preferably 10ms (millisecond) at the most, and this is because if t1 is oversize, because afterimage or blend of colors, colorimetric properties are with variation.And the ratio of t2/t1 is generally at least 2.05, preferably at least 2.07, more preferably at least 2.15, and more preferably at least 2.5, there is no particular limitation to its upper limit, but be about 10 usually.And preferred t1 and t2/t1 satisfy above-mentioned scope.
In addition, even phosphor body of the present invention has chemical composition or the crystal structure identical with conventional phosphor body, since the technicality of processing conditions, its L
*, a
*, b
*Value is also different.
In the phosphor body that contains crystalline phase shown in the formula (1) in being included in second illuminator of the present invention, the starting compound of every kind of element in Ln source, Ce source, Tb source and M source for example is oxide, hydroxide, carbonate, nitrate, sulfate, oxalates, carboxylate or the halide of every kind of element, wherein, for example not producing the performance of halogen, NOx and SOx etc. according to the reactivity of composite oxides, calcining the time waits and selects starting compound.
As the object lesson of the starting compound of Ln, the Y source compound for example is Y
2O
3, Y (OH)
3, YCl
3, YBr
3, Y
2(CO
3)
33H
2O, Y (NO
3)
36H
2O, Y
2(SO
4)
3Or Y
2(C
2O
4)
39H
2O, Gd source compound for example are Gd
2O
3, Gd (OH)
3, GdCl
3, Gd (NO
3)
35H
2O or Gd
2(C
2O
4)
310H
2O, La source compound for example are La
2O
3, La (OH)
3, LaCl
3, LaBr
3, La
2(CO
3)
3H
2O, La (NO
3)
36H
2O, La
2(SO
4)
3Or La
2(C
2O
4)
39H
2O, Sc source compound for example are Sc
2O
3, Sc (OH)
3, ScCl
3, Sc (NO
3)
3NH
2O, Sc
2(SO
4)
3NH
2O or Sc
2(C
2O
4)
3NH
2O, or the Lu source compound for example is Lu
2O
3, LuCl
3, Lu (NO
3)
38H
2O or Lu
2(OCO)
36H
2O.
As the object lesson of M source compound,, for example can mention for example α-Al for Al
2O
3Or γ-Al
2O
3Deng Al
2O
3, Al (OH)
3, AlOOH, Al (NO
3)
39H
2O, Al
2(SO
4)
3Or AlCl
3,, for example can mention Ga for Ga
2O
3, Ga (OH)
3, Ga (NO
3)
3NH
2O, Ga
2(SO
4)
3Or GaCl
3,, for example can mention In for In
2O
3, In (OH)
3, In (NO
3)
3NH
2O, In
2(SO
4)
3Or InCl
3
In addition, as the object lesson of the element source compound of Ce or Tb, the Ce source compound for example is CeO
2, Ce
2(SO
4)
3, Ce
2(CO
3)
35H
2O, Ce (NO
3)
36H
2O, Ce
2(C
2O
4)
39H
2O, Ce (OH)
3Or CeCl
3, or the Tb source compound for example is Tb
4O
7, Tb
2(SO
4)
3, Tb (NO
3)
3NH
2O, Tb
2(C
2O
4)
310H
2O or TbCl
3
Before calcining, these materials are fully mixed to evenly.Particularly, according to circumstances need, compound with the pulverizing of Dry-crushers such as for example kneading machine, stamping mill, ball mill or jet mill Y, Gd, Lu, La, Sc, Ce, Tb, Al, Ga and In mixes fully with for example mixer such as V-mixer or tapered mixer then.But, also can use following method: mix the back and use pulverizer to carry out the method that dry type is pulverized; In media such as for example water, pulverize and mix the method for back drying with wet crushing mill; Or with the method for the dry prepared slurry of spray drying process for example.In these pulverizing and mixed method, especially for the element source compound of centre of luminescence ion, because needing on a small quantity, the element source compound of such centre of luminescence ion all mixes equably and disperses, so preferably use liquid medium, and from obtaining whole angles of mixture uniformly of other element source compound, the such damp process of also preferred use.
Then, the material that fully and equably mixes with one of said method is placed in aluminium oxide for example or the heatproof containers such as quartzy crucible of making or pallet, under common 1000～1700 ℃ calcining heat, heats and calcined 10 minutes to 24 hours.The lower limit of calcining heat is preferably at least 1,100 ℃, and more preferably at least 1,200 ℃, the upper limit is preferably 1,600 ℃ at the most, more preferably at the most 1,550 ℃.Select calcination atmosphere suitably from the air of independent use, nitrogen, argon gas, carbon monoxide, hydrogen or by mixing the gas that nitrogen, argon gas etc. prepare.And the optimum condition of calcining is different with the batch of material, proportion of composing and preparation, but preferred usually reduction calcining.A little less than reduction degree or in the too strong situation, object color can not drop in the object color scope of phosphor body of the present invention.Usually, by atmosphere being adjusted to the phosphor body that great reducing atmosphere can obtain having the object color that the present invention limits.And, select and use for example BaF
2Or AlF
3Can obtain the phosphor body of higher briliancy etc. suitable flux.After heat treatment, if desired, can wash, dispersion treatment, drying, classification etc.
The particle diameter of the employed phosphor body of light-emitting device of the present invention is generally 0.1 μ m～20 μ m.
In the present invention, be used for using up the light that first illuminator that shines above-mentioned phosphor body is launched 420～500nm wavelength, the preferred illuminator of peak wavelength in 450～485nm wave-length coverage that uses the light of being launched.As the object lesson of first illuminator, can mention light emitting diode (LED) or laser diode (LD).From the angle of low energy consumption, more preferably laser diode.Especially, preferably use GaN type LED or LD, they use GaN type compound semiconductor.Because compare with the SiC type LED of the light of for example launching this wave-length coverage, such GaN type LED or LD have significantly high emission output or external quantum efficiency, and by with above-mentioned phosphor body combination, can obtain very bright luminous with quite low electric power.For example, under the current capacity of 20mA, usually the luminous intensity of GaN type LED is 100 times of luminous intensity of SiC type LED at least.Such GaN type LED or LD preferably have Al
xGa
yN luminescent layer, GaN luminescent layer or In
xGa
yThe N luminescent layer.Wherein GaN type LED especially preferably has In
xGa
yThe N luminescent layer, this is that GaN type LD especially preferably has In because luminous intensity is very strong like this
xGa
yThe multiple quantum well structure of N layer or GaN layer, this is because luminous intensity is very strong like this.Here, the value of above-mentioned x+y is usually in 0.8～1.2 scope.Preferred GaN type LED doping of Zn or Si or do not have adulterant in luminescent layer so that regulate the characteristics of luminescence.GaN type LED has such luminescent layer, p layer, n layer, electrode and substrate as the basic element of character, preferably has hybrid structure, and this hybrid structure has the n of being clipped in type and p type Al
xGa
yN layer, GaN layer and In
xGa
yLuminescent layer between the N layer etc. etc., this is because it has high luminous efficiency, more preferably has the multiple quantum well structure to replace hybrid structure, this is because it has higher luminous efficiency.
In the present invention, especially preferably use the surface-emitting type illuminator, especially use the luminous GaN type of face laser diode as first illuminator, because can increase the luminous efficiency of whole light-emitting device like this.The surface-emitting type illuminator is that the film surface has strong luminous illuminator, in the situation of the luminous GaN type of face laser diode, can suppress the crystal growth in luminescent layer etc., and, can strengthen the luminous of luminescent layer surface rather than strengthen the luminous of edge by reflecting layer etc. is handled well.Compare with type with the edge-lit of luminescent layer, use the surface-emitting type illuminator can enlarge the luminous cross-sectional area of unit luminous quantity, the result, in the situation of the phosphor body of using up irradiation second illuminator, can enlarge the irradiated area of the light of same amount significantly, therefore, can increase illumination efficiency, thereby can obtain stronger luminous by phosphor body as second illuminator.
The phosphor body of second illuminator not only can be the phosphor body with the described specific composition of formula (1), and can be to contain the phosphor body of a plurality of different proportion of composing or the phosphor body of the mixture that mixes with other phosphor body, thereby can obtain wideer white light field and the colour rendering index of Geng Gao.There is no particular limitation to described other phosphor body.For example, operable green fluorescent style is as being (Sr, Ca, Mg) Ga
2S
4: Eu or ZnS:Cu, Al, operable red phosphor body for example are (Ca, Sr) S:Eu.And, as reflective agent or dispersant, can use whiteness with phosphor body of the present invention, for example BaSO
4, MgO or CaHPO
4
The method that makes up these phosphor bodies for example is: with each phosphor body lamination of powdered form is membranaceous method; They are blended in the resin, then the method for lamination film forming shape; The method of mixing them with pulverulence; They are dispersed in method in the resin; Their laminations are become the method for film crystal form.The preferred use mixed them with pulverulence and then controlled and use the method for this mixture, because obtain white light with low cost the easiliest the most like this.
In using the situation of surface-emitting type illuminator as first illuminator, preferred second illuminator is membranaceous.The result, light by the emission of surface-emitting type illuminator has enough big cross-sectional area, if second illuminator is membranaceous on this cross-sectional direction, so for the phosphor body of unit quantity, first illuminator will increase the irradiated area of phosphor body, thereby the light intensity that phosphor body sends can further increase.
In addition, using the surface-emitting type illuminator as first illuminator with use in the membranaceous situation of illuminator as second illuminator, preferably adopt the second membranaceous illuminator directly with the light-emitting area contacting structure of first illuminator.Here, described contact is meant that first illuminator closely contacts mutually with second illuminator, does not have the state of air or gas between them.As a result, the light loss of light can be avoided, thereby the luminous efficiency of whole device can be improved because of leaking in the film surface reflection of second illuminator by the emission of first illuminator.
Fig. 2 is first illuminator in the embodiment of expression light-emitting device of the present invention and the perspective schematic view of the position between second illuminator relation.In Fig. 2, Reference numeral 1 expression has the second membranaceous illuminator of above-mentioned phosphor body, and Reference numeral 2 expressions are as the luminous GaN type of the face of first illuminator LD, and Reference numeral 3 is represented substrates.For the state of realizing that they are in contact with one another, can prepare the LD 2 and second illuminator 1 individually, make each surface contact with adhesive or other method then, perhaps second illuminator is formed (being cast into) film on the light-emitting area of LD 2.As a result, can realize the structure that the LD 2 and second illuminator 1 are in contact with one another.
The light that sends by first illuminator or be often referred to all the winds by the light that second illuminator sends, if but the powder of the phosphor body in second illuminator is dispersed in the resin, when light left resin, this light was partly reflected, thereby direction of light is proofreaied and correct to a certain extent.Therefore, can be to a certain extent with this optical alignment on the direction of suitable efficient, therefore, as second illuminator, the preferred use is dispersed in dispersion in the resin with above-mentioned phosphor body powder.And if phosphor body is dispersed in the resin, the illumination of sending with first illuminator entire area of penetrating second illuminator will become greatly so, thereby have the advantage of the luminous intensity that can increase by second illuminator.Employed resin for example is epoxy resin, polyvinyl resin, polyvinyl resin, acrylic resin or mylar in this situation, and preferred epoxy is because such phosphor body powder has excellent dispersiveness.In the powder of second illuminator was dispersed in situation in the resin, the powder of second illuminator was generally 10%～95% with respect to the weight ratio of resin and this total weight of powder, and is preferred 20%～90%, and more preferably 30%～80%.If the amount of phosphor body is too big, because powders, luminous efficiency will reduce, if very little, owing to absorption or the scattering of this resin to light, luminous efficiency will reduce.
Light-emitting device of the present invention comprises the light-emitting component as the light of the above-mentioned phosphor body of material for transformation of wave length and emission 420～500nm wavelength, wherein above-mentioned phosphor body absorbs the light of the 420～500nm wavelength that is sent by light-emitting component, thereby no matter how environment can send high-intensity white light.Such light-emitting device is suitable as the illuminating source of backlight, signalling means or as image display devices such as color liquid crystal display arrangements for example, or the light source of lighting device such as surface illuminating device for example.
Now, describe light-emitting device of the present invention with reference to the accompanying drawings.Fig. 3 is the schematic sectional view of an embodiment that expression has the light-emitting device of first illuminator (illuminator with 420～500nm wavelength) and second illuminator, wherein, Reference numeral 4 expression light-emitting devices, Reference numeral 5 expression support lead-in wires, Reference numeral 6 expression leads, Reference numeral 7 expression first illuminators (illuminator) with 420～500nm wavelength, Reference numeral 8 expressions are as the resin part that contains phosphor body of second illuminator, Reference numeral 9 expression leads, Reference numeral 10 expression profile members.
Light-emitting device as one embodiment of the invention has common bullet shape shown in Figure 3.To be fixed on by first illuminator 7 (illuminator) that GaN type light emitting diode etc. is made in the cup on top of support lead-in wire 5 with 420～500nm wavelength, said fixing is carried out in the resin part that contains phosphor body 8 coverings that are used as the formation of second illuminator by first illuminator 7, the described resin part 8 that contains phosphor body is to be made by following manner: phosphor body is mixed and be dispersed in the adhesive of for example epoxy resin or acrylic resin etc., be cast into described cup then.On the other hand, connect first illuminator 7 and support lead-in wire 5, first illuminator 7 and lead 6 with lead 9 respectively, they all use the shaped component 10 of epoxy resin to cover and protection.
In addition, as shown in Figure 4, the face litillumination devices 11 of light-emitting component 13 is wherein installed in preparation in the following manner: a plurality of light-emitting devices 13 are arranged on the bottom surface of square shell 12, the inner face of this bottom surface is that for example white smooth surface etc. can not see through the surface of light, the (not shown)s such as power supply, circuit that drive light-emitting device 13 are arranged in the outside of this bottom surface, the diffuser plate 14 such as fixing for example milky acrylate plate at the pairing position of the lid of shell 12 then, so as to make luminous evenly.
Drive this face litillumination devices 11, voltage is imposed on first illuminator of this light-emitting component 13, make its light of launching 350～480nm wavelength, the above-mentioned phosphor body that this light is used as in the resin part that contains phosphor body of second illuminator partly absorbs, thereby sends visible light.In addition, visible light and the blue light that is not for example absorbed by phosphor body are carried out colour mixture and obtain the luminous of high-color rendering.This light by diffuser plate 14 to the emission of the top of drawing, thereby in the face of the diffuser plate 14 of shell 12, obtain the illumination light of uniform luminance.
Now, with reference to embodiment the present invention is described in more detail.But, should be appreciated that the present invention is in no way limited to the following example.
In the following example, measure the object color (L of phosphor body with following method herein,
*, a
*, b
*), emission spectrum, total light flux, temperature characterisitic and light-decay characteristic.
Object color
The phosphor body powder is contained in the pond that bore is 10mm Φ, and with colour difference meter (CR-300, by Konica Minolta Holdings, Inc. produces), according to standard light D65 irradiation mode, the synthetic quartz plate thick by 1mm carries out determination of colority, thereby obtains L
*, a
*And b
*
Emission spectrum
Phosphor body is applied on the blue GaN type light-emitting diode chip for backlight unit that dominant wavelength is 465nm, uses spectrometer (by Ocean Photonics, Inc. produces) to measure the emission spectrum when exciting phosphor body.
Total light flux
Being used in combination spectrometer (by Ocean Photonics, Inc. produces) and 1 inch integrating sphere measures.
Temperature characterisitic
Used phosphor body temperature evaluating apparatus (by producing) to foreign electronics society.Can make the MCPD-7000 that produces with big mound electronics society measure luminous intensity.
Light-decay characteristic
Measure with following manner: use nitrogen laser (pulse width: 5ns, frequency: 10Hz, wavelength: 337nm) make excitaton source, at 4 μ W/cm
2Excitating light strength under excite phosphor body, will be with the spectroscope C5094 that Hamamatsu Photonics K.K. produces from the luminous beam split of phosphor body, then, streak camera (streakcamera) C4334 that produces with Hamamatsu Photonics K.K. carries out time-resolved measurement.
For this time-resolved measurement value, nonlinear least square method by " convolution function+constant term ", carry out function match operation, the time constant T1 of gauge index function and T2, their intensity composition A1 and A2 and constant term C to the apparatus function represented by Gaussian function with by the decay of luminescence that two exponential functions are represented.Use these T1, T2, A1, A2 and C, the luminous intensity I (t) that can obtain formula (1) expression can not relied on the light-decay characteristic of apparatus function over time.When intensity become the value of formula (1) when t=0 (exciting the luminous intensity of moment before stopping) 1/10 the time, obtain 1/10 persistence (t1) by this time t, value when intensity becomes formula (1) at t=0 1/100 the time, obtain 1/100 persistence (t2) by this time t.
I(t)＝A1×exp(-t/T1)+A2×exp(-t/T2)+C (1)
Embodiment
Use 1.26 moles of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.33 mole of CeO
2Make the Ce source compound, 0.0375 mole of Tb
4O
7Make the Tb source compound, 0.25 mole of BaF
2Make flux, mix these raw materials fully, then in the crucible that aluminium oxide is made, in containing the nitrogen stream of 4% hydrogen, under 1,450 ℃, calcined 2 hours.Pulverize resulting calcined product, use acid elution, wash with water to remove BaF
2Then, carry out drying and classification and handle, thereby prepare Yellow luminous phosphor body (Y
0.84Ce
0.11Tb
0.05)
3Al
5O
12
The object color of resulting phosphor body is L
*=103.1, a
*=-18.1 and b
*=73.0.Measure the emission spectrum of phosphor body then.This emission spectrum is illustrated among Fig. 1.When resulting total light flux value is as 100% during resulting phosphor body in the Comparative Examples 1 of using the back, based on this, the measured value of the total light flux of resulting phosphor body is 141% in the present embodiment.Temperature characterisitic is 99%.In addition, be 161ns 1/10 persistence (t1), and t2/t1 is 2.11.The result is illustrated in the table 1.
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.79Ce
0.04Tb
0.17)
3Al
5O
12, different is to use 1.185 moles of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.12 mole of CeO
2Make the Ce source compound, 0.1275 mole of Tb
4O
7Make Tb source compound and 0.25 mole of BaF
2Make flux, calcining heat is 1,380 ℃.Estimate resulting phosphor body in the mode identical with embodiment 1, object color is L
*=102.4, a
*=-17.0 and b
*=68.4, total light flux is 131%, and temperature characterisitic is 97%.In addition, t1 is 183ns, and t2/t1 is 2.32.The result is illustrated in the table 1.
Prepare Yellow light emitting phosphor body (Y in the mode identical with embodiment 1
0.45Ce
0.11Tb
0.44)
3Al
5O
12, different be to use 0.675 mole of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.33 mole of CeO
2Make the Ce source compound, 0.33 mole of Tb
4O
7Make Tb source compound and 0.25 mole of BaF
2Make flux, calcining heat is 1,420 ℃.Estimate resulting phosphor body in the mode identical with embodiment 1, object color is L
*=98.9, a
*=-14.0 and b
*=80.0, total light flux is 128%, and temperature characterisitic is 92%.In addition, t1 is 206ns, and t2/t1 is 3.29.The result is illustrated in the table 1.
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.7Gd
0.26Ce
0.04)
3Al
5O
12, different be to use 1.05 moles of Y
2O
3With 0.39 mole of Gd
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.12 mole of CeO
2Make Ce source compound and 0.25 mole of BaF
2Make flux.Estimate resulting phosphor body in the mode identical with embodiment 1, object color is L
*=102.4, a
*=-12.5 and b
*=62.3, total light flux is 120%, and temperature characterisitic is 90%.The result is illustrated in the table 1.
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.96Ce
0.03Tb
0.01)
3Al
5O
12, different be to use 1.44 moles of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.09 mole of CeO
2Make the Ce source compound, 0.0075 mole of Tb
4O
7Make Tb source compound and 0.25 mole of BaF
2Make flux, in nitrogen stream, under 1,400 ℃, calcine.Estimate resulting object color and total light flux in the mode identical with embodiment 1, object color is L
*=102.7, a
*=-14.9 and b
*=58.8, total light flux is 116%.The result is illustrated in the table 1.
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.96Ce
0.04)
3Al
5O1
2, different be to use 1.44 moles of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.12 mole of CeO
2Make Ce source compound and 0.25 mole of BaF
2Make flux, in nitrogen stream, under 1,400 ℃, calcine.Estimate resulting phosphor body in the mode identical with embodiment 1, object color is L
*=101.2, a
*=-14.7 and b
*=57.8, total light flux is 110%, and temperature characterisitic is 98%.In addition, t1 is 151ns, and t2/t1 is 2.03.The result is illustrated in the table 1.
Embodiment 7
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.8Ce
0.1Tb
0.1)
3Al
5O
12, different be to use 1.2 moles of Y
2O
3Make the Ln source compound, 2.5 moles of α-Al
2O
3Make the M source compound, 0.3 mole of CeO
2Make the Ce source compound, 0.075 mole of Tb
4O
7Make Tb source compound and 0.2 mole of BaF
2Make flux, in containing the nitrogen stream of 4% hydrogen, under 1,450 ℃, calcined 3 hours.Estimate the object color and the total light flux of resulting phosphor body in the mode identical with embodiment 1, object color is L
*=105.8, a
*=-15.3 and b
*=95.6, total light flux is 137%.The result is illustrated in the table 1.
Comparative Examples 1
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.7Gd
0.26Ce
0.04)
3Al
5O
12, different be to use 1.05 moles of Y
2O
3With 0.39 mole of Gd
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.12 mole of CeO
2Make Ce source compound and 0.25 mole of BaF
2Make flux, in air, under 1,400 ℃, calcine.Estimate in the mode identical with embodiment 1, object color is L
*=100.0, a
*=-13.3 and b
*=51.4, total light flux is 100%, and temperature characterisitic is 86%.In addition, t1 is 147ns, and t2/t1 is 2.04.The result is illustrated in the table 1.
Comparative Examples 2
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.96Ce
0.03Tb
0.01)
3Al
5O
12, different be to use 1.44 moles of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.09 mole of CeO
2Make the Ce source compound, 0.0075 mole of Tb
4O
7Make Tb source compound and 0.25 mole of BaF
2Make flux, in nitrogen stream, under 1,400 ℃, calcine.Measure object color and total light flux in the mode identical with embodiment 1, object color is L
*=96.0, a
*=-7.6 and b
*=38.4, total light flux is 78%.The result is illustrated in the table 1.
Comparative Examples 3
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.96Ce
0.03Tb
0.01)
3Al
5O
12, different be to use 1.44 moles of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.09 mole of CeO
2Make the Ce source compound, 0.0075 mole of Tb
4O
7Make Tb source compound and 0.25 mole of BaF
2Make flux, in containing the nitrogen stream of 2.5% hydrogen, under 1,400 ℃, calcine.Measure object color and total light flux in the mode identical with embodiment 1, object color is L
*=99.0, a
*=-11.7 and b
*=53.4, total light flux is 100%.The result is illustrated in the table 1.
Comparative Examples 4
Prepare Yellow luminous phosphor body (Y in the mode identical with embodiment 1
0.96Ce
0.03Tb
0.01)
3Al
5O
12, different be to use 1.44 moles of Y
2O
3Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.09 mole of CeO
2Make the Ce source compound, 0.0075 mole of Tb
4O
7Make Tb source compound and 0.25 mole of BaF
2Make flux, in containing the nitrogen stream of 4% hydrogen, under 1,400 ℃, calcine with the carbon pearl.Measure object color and total light flux in the mode identical with embodiment 1, object color is L
*=95.0, a
*=-14.7 and b
*=50.4, total light flux is 90%.The result is illustrated in the table 1.
Comparative Examples 5
Prepare Yellow luminous phosphor body (Ce in the mode identical with embodiment 1
0.11Tb
0.89)
3Al
5O
12, different be to use 0.6675 mole of Tb
4O
7Make the Ln source compound, 2.5 moles of γ-Al
2O
3Make the M source compound, 0.33 mole of CeO
2Make Ce source compound and 0.25 mole of BaF
2Make flux.Estimate in the mode identical with embodiment 1, object color is L
*=95.2, a
*=-9.8 and b
*=77.8, total light flux is 104%, and temperature characterisitic is 88%.The result is illustrated in the table 1.
Table 1
| Phosphor body is formed | Object color | Total light flux (%) | Temperature characterisitic (%) | Light-decay characteristic | |||||
| L * | a * | b * | t1(ns) | t2(ns) | t1/t2 | ||||
| Embodiment 1 | (Y 0.84Ce 0.11Tb 0.05) 3Al 5O 12 | 103.1 | -18.1 | 73.0 | 141 | 99 | 161 | 339 | 2.11 |
| Embodiment 2 | (Y 0.79Ce 0.04Tb 0.17) 3Al 5O 12 | 102.4 | -17.0 | 68.4 | 131 | 97 | 183 | 425 | 2.32 |
| Embodiment 3 | (Y 0.45Ce 0.11Tb 0.44) 3Al 5O 12 | 98.9 | -14.0 | 80.0 | 128 | 92 | 206 | 677 | 3.29 |
| Embodiment 4 | (Y 0.7Gd 0.26Ce 0.04) 3Al 5O 12 | 102.4 | -12.5 | 62.3 | 120 | 90 | - | - | - |
| Embodiment 5 | (Y 0.96Ce 0.03Tb 0.01) 3Al 5O 12 | 102.7 | -14.9 | 58.8 | 116 | - | - | - | - |
| Embodiment 6 | (Y 0.96Ce 0.04) 3Al 5O 12 | 101.2 | -14.7 | 57.8 | 110 | 98 | 151 | 307 | 2.03 |
| Embodiment 7 | (Y 0.8Ce 0.1Tb 0.1) 3Al 5O 12 | 105.8 | -15.3 | 95.6 | 137 | - | - | - | - |
| Comparative Examples 1 | (Y 0.7Gd 0.26Ce 0.04) 3Al 5O 12 | 100.0 | -13.3 | 51.4 | 100 | 86 | 147 | 300 | 2.04 |
| Comparative Examples 2 | (Y 0.96Ce 0.03Tb 0.01) 3Al 5O 12 | 96.0 | -7.6 | 38.4 | 78 | - | - | - | - |
| Comparative Examples 3 | (Y 0.96Ce 0.03Tb 0.01) 3Al 5O 12 | 99.0 | -11.7 | 53.4 | 100 | - | - | - | - |
| Comparative Examples 4 | (Y 0.96Ce 0.03Tb 0.01) 3Al 5O 12 | 95.0 | -14.7 | 50.4 | 90 | - | - | - | - |
| Comparative Examples 5 | (Ce 0.11Tb 0.89) 3Al 5O 12 | 95.2 | -9.8 | 77.8 | 104 | 88 | - | - | - |
By found that of table 1, in embodiments of the invention 1～7, based on the total light flux (100%) of Comparative Examples 1, total light flux all is at least 100%.
Especially, form the contrast of identical embodiment 4 and Comparative Examples 1, find that total light flux has increased by 20% from phosphor body.And embodiment 5 also has identical phosphor body with Comparative Examples 2 and forms, but finds that embodiments of the invention have much higher total light flux.
Here whole disclosures that the Japanese patent application of integrally introducing Japanese patent application 2003-305020 number of submission on August 28th, 2003 by reference and submitting on October 21st, 2003 is 2003-361114 number are comprising specification, claims, accompanying drawing and summary.
Claims (18)
1. light-emitting device with first illuminator and second illuminator, the light of described first illuminator emission, 420～500nm wavelength, when penetrating described second illuminator with the illumination of described first illuminator, described second illuminator is launched visible light, it is characterized in that, described second illuminator contains phosphor body, and the object color of described phosphor body satisfies L
*, a
*, b
*L in the colour system
*〉=90 ,-22≤a
*≤-10 and b
*〉=55.
2. light-emitting device as claimed in claim 1, wherein said phosphor body the luminous intensity under 100 ℃ be at least under 25 ℃ luminous intensity 90%.
3. light-emitting device as claimed in claim 1 or 2, wherein said phosphor body 1/10 persistence t1 be 155ns at least, and/or 1/100 persistence t2 with 1/10 persistence t1 ratio t2/t1 be at least 2.05.
4. as each described light-emitting device in the claim 1～3, wherein said phosphor body comprises oxide and makes parent.
5. light-emitting device as claimed in claim 4, wherein said phosphor body is the oxide with garnet structure, and contains Ce or Ce and Tb.
6. light-emitting device as claimed in claim 5, wherein said phosphor body contain the crystalline phase of chemical composition of (1) expression that has following formula:
(Ln
1-a-bCe
aTb
b)
3M
5O
12Formula (1)
Wherein, Ln is at least a element that is selected from the group of being made up of Y, Gd, Sc, Lu and La, and M is at least a element that is selected from the group of being made up of Al, Ga and In, and a and b are respectively the numerical value that satisfies 0.001≤a≤0.3 and 0≤b≤0.5.
7. light-emitting device as claimed in claim 6, wherein, in formula (1), a satisfies 0.01≤a≤0.2.
8. as each described light-emitting device in the claim 1～7, wherein said first illuminator is laser diode or light emitting diode.
9. light-emitting device as claimed in claim 8, wherein said first illuminator is a laser diode.
10. as each described light-emitting device in the claim 1～9, wherein said first illuminator uses GaN type compound semiconductor.
11. as each described light-emitting device in the claim 1～10, wherein said first illuminator is the luminous GaN type of a face laser diode.
12. as each described light-emitting device in the claim 1～11, wherein said second illuminator is membranaceous.
13. light-emitting device as claimed in claim 12, the film surface of wherein said second illuminator directly contacts with the light-emitting area of described first illuminator.
14. as each described light-emitting device in the claim 1～13, wherein said second illuminator contains other phosphor body, described light-emitting device emission white light.
15. as each described light-emitting device in the claim 1～14, wherein said second illuminator is the illuminator with the phosphor body powder that is dispersed in the resin.
16. as each described light-emitting device in the claim 1～15, wherein said light-emitting device is a lighting device.
17. as each described light-emitting device in the claim 1～15, wherein said light-emitting device is an image display device.
18. a phosphor body is at L
*, a
*, b
*In the colour system, described phosphor body has the L of satisfying
*〉=90 ,-22≤a
*≤-10 and b
*〉=55 object color is characterized in that, described phosphor body contains the crystalline phase of chemical composition of (1) expression that has following formula:
(Ln
1-a-bCe
aTb
b)
3M
5O
12Formula (1)
Wherein, Ln is at least a element that is selected from the group of being made up of Y, Gd, Sc, Lu and La, and M is at least a element that is selected from the group of being made up of Al, Ga and In, and a and b are respectively the numerical value that satisfies 0.001≤a≤0.3 and 0≤b≤0.5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003305020 | 2003-08-28 | ||
| JP305020/2003 | 2003-08-28 | ||
| JP361114/2003 | 2003-10-21 |
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| Publication Number | Publication Date |
|---|---|
| CN1842673A true CN1842673A (en) | 2006-10-04 |
| CN100473895C CN100473895C (en) | 2009-04-01 |
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ID=37031143
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9739444B2 (en) | 2007-03-05 | 2017-08-22 | Intematix Corporation | Light emitting diode (LED) based lighting systems |
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