CN101104802A - Luminescent diode and phosphor thereof - Google Patents

Luminescent diode and phosphor thereof Download PDF

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Publication number
CN101104802A
CN101104802A CNA2007100000459A CN200710000045A CN101104802A CN 101104802 A CN101104802 A CN 101104802A CN A2007100000459 A CNA2007100000459 A CN A2007100000459A CN 200710000045 A CN200710000045 A CN 200710000045A CN 101104802 A CN101104802 A CN 101104802A
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China
Prior art keywords
fluorescent material
matrix
light
particle
yttrium aluminum
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CNA2007100000459A
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Chinese (zh)
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索辛纳姆
罗维鸿
蔡绮睿
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Individual
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Priority to CNA2007100000459A priority Critical patent/CN101104802A/en
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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
    • 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

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Abstract

The invention relates to a phosphor which is prepared with a matrix of yttrium aluminum garnet and an activator of Ce, provided with a composition formula of (Y1-x-y-zGdxCeyBaz)3Al5O12-z/2Fz(x equals to 0.1-0.45, y equals to 0.01-0.08, z equals to 0.0001-0.01). The phosphor radiates greenish yellow light with a peak value changing from 535nm to 585nm in the direct ratio to the concentration ratio of Gd to Y in the matrix of yttrium aluminum garnet. In addition, the invention provides a light-emitting diode whose organic thin film is filled with the phosphor.

Description

Photodiode and fluorescent material thereof
[technical field under the invention]
The present invention system is about a kind of photodiode and fluorescent material thereof, especially refer to a kind of barium ion and fluorion of in composition, having added, photodiode and fluorescent material thereof that the radiation peak of this fluorescent material and Gd in the yttrium aluminum garnet matrix are directly proportional with the concentration ratio (Gd/Y) of Y.
[prior art]
Developing light source, especially white light source, it is a kind of mixed light of many colors, can be by human eye perceives for comprising the mixed light of wavelength more than two kinds at least, when human eye is subjected to the stimulation of red, blue, green glow simultaneously, or all can be felt as white light when being subjected to the stimulation of complementary light such as blue light and gold-tinted simultaneously, so principle can be made and sent light sources of different colors according to this.
In the common technology as the white light solid light source, making method mainly is to utilize light complementary mode, as following several:
First method system uses three solid light sources as material with InGaAlP, GaN and GaP, and the electric current of controlling respectively by solid light source sends red, green and blue light, and the light that will send through lens is mixed and produces white light.
Second method system uses GaN and GaP two solid light sources as material, and it is also controlled electric current by solid light source respectively and sends indigo plant and yellow green light with the generation white light.
But in above-mentioned two kinds of modes, if one of its solid light source breaks down, then can't obtain normal white light, and because of its forward bias has nothing in common with each other, so must overlap pilot circuits, cause cost higher more, this is all the unfavorable factor in the practical application.
Other developed the yttrium aluminum garnet fluorescent substance that with InGaN blue light solid light source cooperation jaundice light as Japanese Ri Ya chemical company (Nichia Chemical) in 1996 also can become a white light source, yet it is for utilizing the complementary color principle to produce white light, the continuity of its spectral wavelength distribution only is suitable as simple lighting use not as real sunlight.The 4th kind of scheme that can produce white light is that (SumitomoElectric Industries Ltd) develops the white light solid light source that uses the ZnSe material to the SUMITOMO CHEMICAL electrician, and it also utilizes light complementary principle to produce white light.
Compared to the technology of above-mentioned known technology generation white light, the present invention utilizes greenish-yellow coloured light solid light source and the fluorescent material with special component to produce various radiating light source especially.
[summary of the invention]
For solving the shortcoming of above-mentioned known technology, the objective of the invention is to produce a kind of fluorescent material, it has added barium ion and fluorion in composition, the radiation peak of this fluorescent material is directly proportional with the concentration ratio (Gd/Y) of Y with Gd in the yttrium aluminum garnet matrix.
For solving the shortcoming of above-mentioned known technology, another object of the present invention is to produce a kind of fluorescent material, and it is radiation-curable to go out greenish-yellow coloured light and its radiation peak and move to the 585nm wave band in λ=535.
For solving the shortcoming of above-mentioned known technology, another object of the present invention is to make a kind of photodiode, and it is filled with fluorescent material, is 100～1000cd to be formed on radiation half-angle 2 θ place light intensity, and colour temperature is the greenish-yellow coloured light of the radiation of 2800～12000K.
For achieving the above object, the present invention relates to a kind of fluorescent material, it is to be matrix with the yttrium aluminum garnet, and Ce makes the fluorescent material of exciting agent, and it has added barium ion and fluorion in forming, and the formation chemical formula is (Y 1-x-y-zGd xCe yBa z) 3Al 5O 12-z/2F zCompound, x=0.1～0.45 wherein, y=0.01～0.08, z=0.0001～0.01, wherein the radiation peak of this fluorescent material is directly proportional with the concentration ratio (Gd/Y) of Y with Gd in this yttrium aluminum garnet matrix.
For achieving the above object, the present invention relates to a kind of photodiode, it is by InGaN shortwave heterojunction, is filled with as mentioned above that the organic thin film layer and the spherical lens of fluorescent material constitute, and wherein the matrix of this organic film is made of the heat-coagulation compound.
[embodiment]
The present invention discloses a kind of photodiode and fluorescent material thereof, and this fluorescent material is for example and without limitation to inorganic fluorescent powder, it is matrix with the yttrium aluminum garnet, Ce makes exciting agent, and in composition, having added barium ion and fluorion, the radiation peak of this fluorescent material is directly proportional with the concentration ratio (Gd/Y) of Y with Gd in this yttrium aluminum garnet matrix.
Wherein, the chemical constitution of the matrix of this fluorescent material is for example and without limitation to (Y 1-x-y-zGd xCe yBa z) 3Al 5O 12-z/2F zYttrium aluminum garnet, and use Ce to make exciting agent, this fluorescent material is radiation-curable to go out greenish-yellow coloured light, radiation peak moves to the 585nm wave band in λ=535, and with the yttrium aluminum garnet matrix in Gd be directly proportional with the concentration ratio (Gd/Y) of Y.Wherein, the basic chemical formula (Y of this fluorescent material 1-x-y-zGd xCe yBa z) 3Al 5O 12-z/2F zMiddle x=0.1～0.45, y=0.01～0.08, z=0.0001～0.01.Wherein, this fluorescent powder grain is 15～20% to λ=440 to the minimal reflection coefficient of the light of 450nm wave band.
This fluorescent powder grain is similar to ellipse, and its average particle size is d 50=10～20 microns, have the dodecahedral crystal framework of hexagon, dodecahedral rib length depends on F ionic concentration in the particle, increase with the increase of F ionic concn, and its density is at d=2.8～3.2g/cm 3And it is ZnOnSiO that this fluorescent powder grain surface coverage has moiety 2The silicate of Zn, n=1 or 2 wherein, the active ion concentration of its particle surface is 10 6～10 7G/l.
This fluorescent powder grain has the garnet cubes micro-architecture of monocrystalline, under the irradiation of X-ray, the main peak value area of its principal plane (hkl)=(420) is less than 550 units, the angle of half high half-breadth is 3 degree, lattice parameter d=12.05A, and its particulate faceted pebble to the reflection of light coefficient of λ=530nm up to more than 80%.
The single crystal particle of this fluorescent material has intensive X-ray framework peak value when X ray becomes 18.1 degree angles with plane (hkl)=(211), intensity reaches 40～43%, and the intensity when becoming 3 3.4 degree angles with plane (hkl)=(420) is 100%.
During Ce ionic concn (Ce)=0.015 atomic fraction in the yttrium aluminum garnet matrix of this fluorescent material, this fluorescent material is by the spectral half-width Δ λ=118nm of the luminous stimulated luminescence of shortwave heterojunction, and when working as (Ce)=0.04 atomic fraction, spectral half-width Δ λ=122nm.Ba ionic concn (Ba) in this yttrium aluminum garnet matrix is when 0.005 atomic fraction increases to 0.01 atomic fraction, and its luminous sunset glow length is from τ eHow=120 increase to two times of original τ second eHow second=240.
Fluorescent material of the present invention has following feature: it is matrix with the yttrium aluminum garnet, it has added barium ion and fluorion in forming, the proportionlity of barium ion and fluorion is in z=0.0001～0.01 variation, and the radiation peak of this fluorescent material is directly proportional with the concentration ratio (Gd/Y) of Y with Gd in this yttrium aluminum garnet matrix.
In addition, the present invention further provides a kind of photodiode.Please refer to Fig. 1, it illustrates the light-emitting diode structure synoptic diagram of a preferred embodiment of the present invention.As shown in the figure, photodiode of the present invention by InGaN shortwave heterojunction 1, be filled with as mentioned above that the organic thin film layer 2 and the spherical lens 3 of fluorescent material constitute, wherein the matrix of this organic film 2 is made of the heat-coagulation compound.
Wherein, this fluorescent material has aforesaid characteristic and composition, so do not intend giving unnecessary details at this.This heat-coagulation compound can be such as but not limited to silicone resin, Resins, epoxy or polycarbonate.The filling concentration of this fluorescent powder grain in this organic thin film layer 2 is 10～70%, and film concentration is 50～200 microns.Wherein, this spherical lens 3 transmits the luminous organic thin film layer 2 that is filled with this fluorescent material that sees through of heterojunction semiconductor 1 come out, the geometric centre of the main light-emitting area of the optical axis of this spherical lens 3 and this heterojunction semiconductor 1 coincides, being formed on radiation half-angle 2 θ place light intensity is 100～1000cd, and colour temperature is the radiation of 2800～12000K.
In sum, the present invention relates to a kind of photodiode and fluorescent material thereof, it is matrix with the yttrium aluminum garnet, Ce makes exciting agent, it has added barium ion and fluorion in forming, the radiation peak of this fluorescent material is directly proportional with the concentration ratio (Gd/Y) of Y with Gd in this yttrium aluminum garnet matrix, therefore, really can improve the shortcoming of known diode fluorescent powder.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limit the present invention; anyly have the knack of this skill person; without departing from the spirit and scope of the present invention; when the change that can do a little and retouching, so protection scope of the present invention is as the criterion when looking the scope that the accompanying Claim book defined.
[accompanying drawing simple declaration]
Fig. 1 is a synoptic diagram, and it illustrates the light-emitting diode structure synoptic diagram of a preferred embodiment of the present invention.
[primary clustering nomenclature]
InGaN shortwave heterojunction 1 organic thin film layer 2
Spherical lens 3

Claims (17)

1. fluorescent material, it is a matrix with the yttrium aluminum garnet, and cerium is made exciting agent, and it has added barium ion and fluorion in forming, and the formation chemical formula is (Y 1-x-y-ZGd xCe yBa z) 3Al 5O 12-z/2F zCompound, x=0.1～0.45 wherein, y=0.01～0.08, z=0.0001～0.01, wherein the radiation peak of this fluorescent material is directly proportional with the concentration ratio of Y with Gd in this yttrium aluminum garnet matrix.
2. fluorescent material as claimed in claim 1, it is radiation-curable to go out greenish-yellow coloured light.
3. fluorescent material as claimed in claim 1, its radiation peak move to the 585nm wave band in λ=535.
4. fluorescent material as claimed in claim 1, its particle is similar to ellipse, and its average particle size is d 50=10～20 microns, have the dodecahedral crystal framework of hexagon, dodecahedral rib length depends on the concentration of fluorion in the particle, increases with the increase of fluorinion concentration.
5. fluorescent material as claimed in claim 1, it has the garnet cubes micro-architecture of monocrystalline, and under the irradiation of X-ray, the main peak value area of its principal plane (hkl)=(420) is less than 550 units, and the angle of half high half-breadth is 3 degree, lattice parameter d=12.05A.
6. fluorescent material as claimed in claim 4, its particulate faceted pebble to the reflection of light coefficient of λ=530nm up to more than 80%.
7. fluorescent material as claimed in claim 1, its particle is 15～20% to λ=440 to the minimal reflection coefficient of the light of 450nm wave band.
8. fluorescent material as claimed in claim 1, its single crystal particle has intensive X-ray framework peak value when X ray becomes 18.1 degree angles with plane (hkl)=(211), intensity reaches 40～43%, and the intensity when becoming 33.4 degree angles with plane (hkl)=(420) is 100%.
9. fluorescent material as claimed in claim 1, wherein during the Ce ionic concn in this yttrium aluminum garnet matrix=0.015 atomic fraction, this fluorescent material is by the spectral half-width Δ λ=118nm of the luminous stimulated luminescence of shortwave heterojunction, and when Ce ionic concn=0.04 atomic fraction, spectral half-width Δ λ=122nm.
10. fluorescent material as claimed in claim 1, wherein the Ba ionic concn in this yttrium aluminum garnet matrix is when 0.005 atomic fraction increases to 0.01 atomic fraction, and its luminous sunset glow length is from τ eHow=120 increase to two times of original τ second eHow second=240.
11. fluorescent material as claimed in claim 1, its particle is rounded, and density is at d=2.8～3.2g/cm 3
12. it is ZnO nSiO that fluorescent material as claimed in claim 1, its particle surface are coated with moiety 2The silicate of Zn, n=1 or 2 wherein.
13. fluorescent material as claimed in claim 1, the active ion concentration of its particle surface is 10 6～10 7/ l.
14. a photodiode, it is made of InGaN shortwave heterojunction, the organic thin film layer that is filled with fluorescent material described in claim 1 and spherical lens, and wherein the matrix of this organic film is made of the heat-coagulation compound.
15. photodiode as claimed in claim 14, wherein this heat-coagulation compound can be silicone resin, Resins, epoxy or polycarbonate.
16. photodiode as claimed in claim 14, wherein the filling concentration of this fluorescent powder grain is 10～70%, and film concentration is 50～200 microns.
17. photodiode as claimed in claim 14, wherein this spherical lens transmits out with the luminous organic thin film layer that is filled with this fluorescent material that sees through of heterojunction semiconductor, the geometric centre of the optical axis of this spherical lens and the main light-emitting area of this heterojunction semiconductor coincides, being formed on radiation half-angle 2 θ place light intensity is 100～1000cd, and colour temperature is the radiation of 2800～12000K.
CNA2007100000459A 2007-01-08 2007-01-08 Luminescent diode and phosphor thereof Pending CN101104802A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604634A (en) * 2012-02-10 2012-07-25 南通南京大学材料工程技术研究院 Yellow fluorescent powder for white light emitting diode (LED)
CN102748595A (en) * 2011-04-19 2012-10-24 展晶科技(深圳)有限公司 Light emitting diode (LED) light source device
CN102936497A (en) * 2012-11-08 2013-02-20 广州有色金属研究院 Main emission peak changeable and adjustable fluorescent material and preparation method thereof
CN104745189A (en) * 2013-12-26 2015-07-01 奇美实业股份有限公司 Phosphor and light emitting device
US9884991B2 (en) 2013-12-26 2018-02-06 Chi Mei Corporation Phosphor, preparing method for phosphor, and light emitting device

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102748595A (en) * 2011-04-19 2012-10-24 展晶科技(深圳)有限公司 Light emitting diode (LED) light source device
CN102604634A (en) * 2012-02-10 2012-07-25 南通南京大学材料工程技术研究院 Yellow fluorescent powder for white light emitting diode (LED)
CN102604634B (en) * 2012-02-10 2013-08-28 南通南京大学材料工程技术研究院 Yellow fluorescent powder for white light emitting diode (LED)
CN102936497A (en) * 2012-11-08 2013-02-20 广州有色金属研究院 Main emission peak changeable and adjustable fluorescent material and preparation method thereof
CN104745189A (en) * 2013-12-26 2015-07-01 奇美实业股份有限公司 Phosphor and light emitting device
CN104745189B (en) * 2013-12-26 2017-07-28 奇美实业股份有限公司 Phosphor and light emitting device
US9884991B2 (en) 2013-12-26 2018-02-06 Chi Mei Corporation Phosphor, preparing method for phosphor, and light emitting device

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Open date: 20080116