CN101712871B - White light luminous diode and iodide garnet phosphor powder thereof - Google Patents
White light luminous diode and iodide garnet phosphor powder thereof Download PDFInfo
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- CN101712871B CN101712871B CN2009101785889A CN200910178588A CN101712871B CN 101712871 B CN101712871 B CN 101712871B CN 2009101785889 A CN2009101785889 A CN 2009101785889A CN 200910178588 A CN200910178588 A CN 200910178588A CN 101712871 B CN101712871 B CN 101712871B
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- iodide
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention relates to a white light luminous diode and iodide garnet phosphor powder thereof, wherein the iodide garnet phosphor powder takes a rare earth oxide element of a garnet framework as a matrix. The iodide garnet phosphor powder is characterized in that iodide ions I-1 and silicon ions Si+4 are added and introduced to the phosphor powder material, and electrons are compensated mutually in anion crystal lattices, thereby forming the following chemometry formula: (SigmaLn)3Al2[Al1-xSixO4-xIx)]3, wherein SigmaLn is equal to Y and/or Gd and/or Tb and/or Lu and/or La and/or Ce and/or Pr; the radiation wave of the phosphor powder can generate long wave displacement under the excitation of an InGaN semiconductor heterojunction. In addition, the invention also discloses a method for preparing the iodide garnet phosphor powder.
Description
Technical field
The present invention relates to a kind of electronic technology field, refer in particular to a kind of iodide garnet phosphor powder relevant with the lighting engineering that broadly is called as " solid state light emitter " (Solid state lighting) and use the white light emitting diode of this iodide garnet phosphor powder.
Background technology
Semiconductor light-emitting-diode was developed rapidly at nearly 50 years, engineers has been developed the material take GaAs-GaP as matrix, be mainly infrared light and ruddiness, add the fluorescent material that is called anti-Stokes, absorb infrared radiation, inspire again visible light (please refer to S.Berg A.DinB light emiting diod (LED) " Mir " Moskow P625.1992), but such photodiode usefulness very low (for ° angle, 2 θ=30, being no more than I=0.1cd).This technology uses scope very narrow.
Japanology personnel S.Nakanura (please refer to the Blue laser of S.Nakamura, BerligSpringer, 1997) the leading special high efficiency energy subrack structure photodiode that contains take nitride InGaN as matrix that produces, this can make the outside efficiency propagation nearly 50% that takes out, this technology adopts traditional stokes fluorescent material, and its radiation wavelength is greater than excitation wavelength.First such a semiconductor light-emitting-diode (please refer to all US Patent No. of Y.Schimizu 6 in 20 end of the centurys by Japan " Nichia " company, 069,440,2000/05/30) propose, the physical structure that the semi-conductor white light emitting diode that this patent discloses adopts is as follows: 1. stokes inorganic light-emitting fluorescent material is subjected to that the shortwave heterojunction is luminous to be excited; 2. form two kinds of independently light sources, such as the blueness of heterojunction radiation and the yellow of fluorescent material radiation, can form white light.The theory that the white light radiation produces is from newton's complementary color principle; And the blue ray radiation of 3. heterojunction with have a yttrium aluminum garnet Y
3Al
5O
12: the yellow radiation fluorescent material of Ce interosculates, this material development (please refer to G.Blasse Luminescence Materials Springer-Verlag the sixties in 20th century [Blasse G], Amst, NY, and be used to make in radioactivity electronic machine and the scintillator P.380.1994.).
With the heterogeneous white light emitting diode of becoming the basis of InGaN, when penetrating the multi-lager semiconductor framework, stream of electrons produces injection electroluminescence, have quantum radiation light when the electroluminescent that produces in the heterojunction layer combines with thulium, energy approaches is prohibited range parameter Eg=2.6eV.Fluorescent material Y
3Al
5O
12: the Ce absorbing wavelength is the blue light of λ=450～470nm, the yellow of radiation wavelength λ=540～560nm.
Luminescent conversion layer is the distribution that contains fluorescent material in the transparent polymeric layer.Describe each light-emitting area of all particles in detail, in the non-absorbent heterojunction blue ray radiation of the part formation white-light spectrum that combines with luminous radiation that fluorescent material is excited, its key coat is to be combined into by blue color spectrum and yellow spectrum.The chemometric equation that contains rare earth element is: (∑ Lu)
3Al
2(AlO
4)
3And natural mineral matter garnet crystal framework.160 atoms are arranged in garnet crystal lattice, and overall ligancy is K=8.Have the characteristics of luminescence of garnet framework and the active element of in component, introducing, for example Eu for increase
+ 3, Tb
+ 3Or Ce
+ 3
The fluorescent material of garnet framework be with cerium as activator, the contriver has pointed out to adopt for the first time effective scintillator of G.Blass, and with development the sixties in 20th century [Blasse G] and by with make scintillator and with as the cathodeluminescence ray contain Y
3Al
5O
12: the equipment of Ce, exactly, the present application people is according to US6, has bright luminous after being excited by blue ray radiation in the pointed luminescent material of 069,440 patent in wavelength X=540～560nm yellow-green colour and yellow area.In conjunction with two kinds of luminous radiations, first step blue ray radiation and second stage gold-tinted radiation, the complementary color principle according to newton draws strong white light.
Yet this US6, still there is a series of defective in 069,440 patent, 1. points out to be positioned at InGaN heterojunction and Y that is:
3Al
5O
12: the fixedly colour temperature of Ce, such colour temperature is called cold white light usually on optical technology, for quoting professional special theory: colour temperature T＞8000K and special chromaticity coordinates x=0.31, y=0.31 (for system MKO1931); 2. the second, for the restriction of relevant such photodiode, adopt low effective quantum efficiency η≤0.75.Its reason be at the effective luminescent phosphor YAG take white light emitting diode as matrix at electric current I=300～700mA, luminous efficiency is 20～40 lumens/watt; The 3rd, the photodiode framework of knowing and inorganic fluorescent powder deficiency in essence, the formation of its luminescence converter is that the thermostability of radiation light emitting diode is low, effective luminous minimizing 10～15% during in temperature T=85 ℃.
Similarly, exist equally deficiency at other serial garnet phosphor powder, for example expensive, must adopt very highly purified starting materials (99.999%), in addition, the synthetic of fluorescent material must carry out heat treatment with 1600 ℃ high temperature.
Such condition is so that the fluorescent powder grain degree that obtains in building-up process is large.Get rid of the deficiency of the nanometer garnet phosphor powder of knowing, composition is (Y, A)
3(Al, B)
5(O, C)
12(please refer to US20080138268 A1 patent application).
Corresponding with the prototype of above-mentioned patent, the Y of the data that disclose in the positively charged ion lattice be by ion A=Gd, Tb, Lu, Sm, Sr, Ba, Ca replaces, perhaps in anion lattice Al by B=Si, Ge, B, P replaces, or O is by C=F, Cl, N replaces.The replacement that discloses in US 200813828 patent applications (please refer to the people's such as TaoDejie U.S. US 200813828 patent applications, 2008/06/12) is to increase permission maximum spectral wavelength λ=540～560nm displacement in the situation that guarantee luminosity.
Analyze the major defect that exists in the data of above-mentioned patent application.At first, the described most of ion alternative patterns of patent documentation are used in experiment.As how replacing Tb, Gd, Sm, La, Sr, Ba, Ca, Mg, B, Si, Ge, F and N, the second, all enter Y simultaneously
3Al
5O
12: the unreasonable element of Ce component will cause the luminosity of fluorescent material to descend.The 3rd, for the method that must adopt gel (colloidal sol) technology of obtaining of minitype particle fluorescent material, the process of the fluorescent material of producing is very complicated.
Summary of the invention
For solving the shortcoming of above-mentioned known techniques, main purpose of the present invention provides a kind of iodide garnet phosphor powder, and it can form the method that changes fluorescent material spectrum, guarantees that the cold white that photodiode has a standard sends out.
For solving the shortcoming of above-mentioned known techniques, another object of the present invention provides a kind of iodide garnet phosphor powder, and it is the fluorescent material that can determine to increase effective quantum radiation.
For solving the shortcoming of above-mentioned known techniques, another object of the present invention provides a kind of iodide garnet phosphor powder, its when promoting the heat treatment of instrument, special fluorescent material radioluminescence and the stability of natural light in its equipment.
For solving the shortcoming of above-mentioned known techniques, another object of the present invention provides a kind of white light emitting diode, and it is from reducing in essence working temperature, and secondly another research direction is to use luminescent conversion layer to create miniature fluorescent powder grain.
For reaching above-mentioned purpose, iodide garnet phosphor powder of the present invention be rare earth oxide element take the garnet framework as matrix, it is characterized in that: in this phosphor material powder, add and introduce iodide ion I
-1And silicon ion Si
+ 4, mutual compensate for electronic forms following chemometric equation: (∑ Ln) in the anion lattice
3Al
2(Al
1-xSi
xO
4-xI
x)
3, wherein ∑ Ln=Y and/or Gd and/or Tb and/or Lu and/or La and/or Ce and/or Pr; This fluorescent material radiation can produce the long wave displacement under the exciting of an InGaN heterojunction semiconductor.
In order to achieve the above object, a kind of white light emitting diode of the present invention is as matrix take heterojunction semiconductor InGaN, and scribble a luminescent conversion layer, this luminescent conversion layer is distributed on this heterojunction radiating surface and the faceted pebble, and be added with aforesaid fluorescent material in this luminescent conversion layer, it is characterized in that: the variation in thickness scope in this luminescent conversion layer is 80～200 microns, and even thickness.
Description of drawings
Fig. 1 a is the spectral distribution graph of the radiation spectrum of sample 1 in the table 1, Fig. 1 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 1 in the table 1, they are recorded by SPR-920D fluorescent material optical color parameter overall analysis system (by Three-Colour Instrument Co., Ltd., Zhejiang Univ.'s development), and gained fluorescent material optical color parameter analytical test report (Spectroradiometric Analysis Report forPhosphor) is as follows:
Name of product Product:C-223-a1-1455c-465nm-20ma
The Manufacturer of manufacturers:
Customer name Client:
Sample number into spectrum Sample No.: testDate Date:2008 July 9
Tester Tested By: auditor Reviewed By:
Test condition Test Condition
Probe temperature Temperature: ℃ relative humidity RH:%
Reference gain Ref.Gain:64 spectrum gain Spe.Gain:4
Spectral range Spectrum Range:380-780nm sampling interval Scan Step:5nm
Optical color parameter Spectroradiometric Parameters
Chromaticity coordinate Chromaticity Coordinates:x=0.3960 y=0.4536 u=0.207 v=0.3557
Correlated(color)temperature Correlated Color Temperature:4105K
Brightness Brightness:23051.5
With reference to white light Reference White:C light source peak wavelength Peak Wavelength:560.8nm
Predominant wavelength Dominant Wavelength:571nm spectral bandwidth Bandwidth:119.8nm
Purity of color Purity:0.6024 radiance Radiant Brightness:60.735
Color ratio Color Ratio:Kr=44.7% Kg=36.0% Kb=19.3%
Colour rendering index Rendering Index:Ra=65.8
R1＝58 R2＝74 R3＝91 R4＝56 R5＝55 R6＝64 R7＝83 R8＝44
R9＝-58 R10＝40 R11＝46 R12＝23 R13＝62 R14＝94 R15＝48
Fig. 2 a is the spectral distribution graph of the radiation spectrum of sample 2 in the table 1, Fig. 2 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 2 in the table 1, they are recorded by SPR-920D fluorescent material optical color parameter overall analysis system (by Three-Colour Instrument Co., Ltd., Zhejiang Univ.'s development), and gained fluorescent material optical color parameter analytical test report (Spectroradiometric Analysis Report forPhosphor) is as follows:
Name of product Product:C-225-a1-1455c-465nm-20ma
The Manufacturer of manufacturers:
Customer name Client:
Sample number into spectrum Sample No.: testDate Date:2008 July 9
Tester Tested By: auditor Reviewed By:
Test condition Test Condition
Probe temperature Temperature: ℃ relative humidity RH:%
Reference gain Ref.Gain:64 spectrum gain Spe.Gain:4
Spectral range Spectrum Range:380-780nm sampling interval Scan Step:5nm
Optical color parameter Spectroradiometric Parameters
Chromaticity coordinate Chromaticity Coordinates:x=0.3866 y=0.4382 u=0.2066 v=0.3513
Correlated(color)temperature Correlated Color Temperature:4222K
Brightness Brightness:22745.5
With reference to white light Reference White:C light source peak wavelength Peak Wavelength:562.4nm
Predominant wavelength Dominant Wavelength:571nm spectral bandwidth Bandwidth:121.6nm
Purity of color Purity:0.5354 radiance Radiant Brightness:62.019
Color ratio Color Ratio:Kr=43.8% Kg=34.4% Kb=21.8%
Colour rendering index Rendering Index:Ra=68.1
R1＝61 R2＝77 R3＝93 R4＝57 R5＝58 R6＝68 R7＝83 R8＝47
R9＝-50 R10＝47 R11＝49 R12＝30 R13＝66 R14＝95 R15＝52
Fig. 3 a is the spectral distribution graph of the radiation spectrum of sample 3 in the table 1, Fig. 3 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 3 in the table 1, they are recorded by SPR-920D fluorescent material optical color parameter overall analysis system (by Three-Colour Instrument Co., Ltd., Zhejiang Univ.'s development), and gained fluorescent material optical color parameter analytical test report (Spectroradiometric Analysis Report forPhosphor) is as follows:
Name of product Product:C-256-a1-1455c-465nm-20ma
The Manufacturer of manufacturers:
Customer name Client:
Sample number into spectrum Sample No.: testDate Date:2008 July 10
Tester Tested By: auditor Reviewed By:
Test condition Test Condition
Probe temperature Temperature: ℃ relative humidity RH:%
Reference gain Ref.Gain:64 spectrum gain Spe.Gain:4
Spectral range Spectrum Range:380-780nm sampling interval Scan Step:5nm
Optical color parameter Spectroradiometric Parameters
Chromaticity coordinate Chromaticity Coordinates:x=0.4203 y=0.4600 u=0.219 v=0.3594
Correlated(color)temperature Correlated Color Temperature:3685K
Brightness Brightness:26359.5
With reference to white light Reference White:C light source peak wavelength Peak Wavelength:568.7nm
Predominant wavelength Dominant Wavelength:573nm spectral bandwidth Bandwidth:120.4nm
Purity of color Purity:0.6817 radiance Radiant Brightness:69.589
Color ratio Color Ratio:Kr=49.9% Kg=35.2% Kb=15.0%
Colour rendering index Rendering Index:Ra=65.1
R1＝58 R2＝73 R3＝88 R4＝57 R5＝54 R6＝61 R7＝85 R8＝45
R9＝-52 R10＝37 R11＝45 R12＝19 R13＝61 R14＝93 R15＝50
Fig. 4 a is the spectral distribution graph of the radiation spectrum of sample 4 in the table 1, Fig. 4 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 4 in the table 1, they are recorded by SPR-920D fluorescent material optical color parameter overall analysis system (by Three-Colour Instrument Co., Ltd., Zhejiang Univ.'s development), and gained fluorescent material optical color parameter analytical test report (Spectroradiometric Analysis Report forPhosphor) is as follows:
Name of product Product:BW68812-2-a1-1475c-465nm-20ma
The Manufacturer of manufacturers:
Customer name Client:
Sample number into spectrum Sample No.: testDate Date:2008 August 2
Tester Tested By: auditor Reviewed By:
Test condition Test Condition
Probe temperature Temperature: ℃ relative humidity RH:%
Reference gain Ref.Gain:64 spectrum gain Spe.Gain:2
Spectral range Spectrum Range:380-780nm sampling interval Scan Step:5nm
Optical color parameter Spectroradiometric Parameters
Chromaticity coordinate Chromaticity Coordinates:x=0.4458 y=0.4231 u=0.2481 v=0.3533
Correlated(color)temperature Correlated Color Temperature:3007K
Brightness Brightness:20349.9
With reference to white light Reference White:C light source peak wavelength Peak Wavelength:609.8nm
Predominant wavelength Dominant Wavelength:580nm spectral bandwidth Bandwidth:127.6nm
Purity of color Purity:0.6506 radiance Radiant Brightness:61.541
Color ratio Color Ratio:Kr=59.3% Kg=27.5% Kb=13.2%
Colour rendering index Rendering Index:Ra=68.9
R1＝64 R2＝80 R3＝91 R4＝58 R5＝59 R6＝67 R7＝82 R8＝49
R9＝-21 R10＝50 R11＝43 R12＝33 R13＝66 R14＝94 R15＝62
Fig. 5 is the configuration diagram according to the white light emitting diode of iodide garnet phosphor powder made of the present invention.
Fig. 6 is the schematic diagram of the X ray of sample 3 in the table 1.
Embodiment
At first, the shortcoming that the object of the invention is to eliminate above-mentioned fluorescent material and use the white light emitting diode of this fluorescent material.In order to reach this target, rare-earth iodide garnet phosphor powder of the present invention be rare earth oxide element take the garnet framework as matrix, it is characterized in that: in this phosphor material powder, add and introduce iodide ion I
-1And silicon ion Si
+ 4, mutual compensate for electronic forms following chemometric equation: (∑ Ln) in the anion lattice
3Al
2(Al
1-xSi
xO
4-xI
x)
3, wherein ∑ Ln=Y and/or Gd and/or Tb and/or Lu and/or La and/or Ce and/or Pr; This fluorescent material radiation can produce the long wave displacement under the exciting of an InGaN heterojunction semiconductor.
Wherein, this stoichiometry index is 0.0001＜x≤0.10.
Wherein, this long wave displacement is Δ 〉=25nm.
Wherein, as follows at the component of anion lattice rare earth elements ion: 0.5≤Y/ ∑ Ln≤0.95; 0.01≤Gd/ ∑ Ln≤0.5; 0.001≤Tb/ ∑ Ln≤0.05; 0.001≤Lu/ ∑ Ln≤0.05; 0.001≤La/ ∑ Ln≤0.05; 0.01≤Ce/ ∑ Ln≤0.1; 0.001≤Dy/ ∑ Ln≤0.05; 0.0001≤Pr/ ∑ Ln≤0.05.
Wherein, this fluorescent material has garnet cubic crystal framework, increases iodide ion I in its anion lattice
-1And silicon ion Si
+ 4Concentration, lattice parameter then can increase, a 〉=12.08A.
Wherein, this fluorescent material is for (Y
0.95Tb
0.01Ln
0.01Ce
0.03)
3Al
2[Al
0.99Si
0.01O
3.99I
0.01]
3Component, that is add iodide ion I
-1With silicon ion Si
+ 4, spectrum maximum value λ=560nm, the wide λ of curve of spectrum half-wave
0.5=119nm.
Wherein, the particle form of this fluorescent material is ellipse, and has special crystallite framework, neutrality line diameter d
50≤ 2 microns, d
90≤ 8 microns.
Then will explain the physical-chemical property of iodide garnet phosphor powder proposed by the invention.The first, how iodide garnet phosphor powder proposed by the invention aluminium garnet in the cubic(al)grating framework is replaced, and namely is like this equally in anion lattice.In the positively charged ion lattice, ion Y
+ 3By Gd
+ 3, Tb
+ 3, Lu
+ 3Or La
+ 3Replace, have simultaneously active ions Ce
+ 3And/or Dy
+ 3And/or Pr
+ 3
The replacement type of indication belongs to Gauss's Law, and rare earth ion proposed by the invention has identical degree of oxidation+3, mainly gets for Y
+ 3Ion.
In anion lattice, replace and be created in Al
+ 3Ion and Si
+ 4Between the ion.This form is positioned at different valence state replaces, and novel point defect (Si occurs
Al) ° have effective quantum and fill.
Simultaneously, at tetrahedron [AlO
4] middle oxonium ion O partly
-2Equally by iodide ion I
-1Replace, such form is replaced and still is positioned at different valence state, the central point (I that sets up
o) ', has effective unit and loads.And the replacement of this form is arranged in scope of equal value so this ion I
-1Size (the radius size τ of iodide ion
I=2.20A) be replaced ion O
-2Size (τ
O=1.38-1.4A), in the applicant's US200727845 U.S. Patent application, do not monitor such replacement type.
At this, the application discloses equally, and the different valence state that produces in the negatively charged ion lattice is like this replaced in same tetrahedral scope.The silicon ion Si that different like this valency is replaced
+ 4With iodide ion I
-1In same tetrahedron, compare iodide ion I
-1(the radius size τ of iodide ion
I=2.20A) be replaced oxonium ion O
-2Size (τ
O=1.38～1.40A), silicon ion Si
+ 4(τ
Si=0.48～0.52A) and aluminum ion Al
+ 3(τ
Al=0.62A), can draw the larger iodide ion of permission and be configured in [Al in the tetrahedron coordinate
1-xSi
xO
4-xI
x]
3
Can find out that its physical properties should be that heterojunction different in the result is replaced.At first, in the end should increase lattice parameter " a " with this similar replacement is connected with the macrobead crystallographic system of its preservation; The second, with first closely-related be that the maximum spectral radiance of fluorescent material is displaced to orange red luminous field.With the replacement of non-equivalence ion, manifest the wide λ of spectral radiance half-wave like this
0.5Widen.The performance of non-equivalent replacement in described graphic representation should have different width on the left side and the right of Gaussian curve figure.
In the instrument that assembles, has power supply U=3.4V and electric current I=20～1700mA.After passing the instrument euphotic cover, produce white light, determine the characteristic of its color.What equally, the special radiation of this instrument was quoted is the warm white that naked eyes are accepted.
Here be to adopt inorganic fluorescent powder to its substantial advantage of semiconductor subassembly proposed by the invention, be characterised in that: the component of the rare earth element of its composition in the positively charged ion lattice is:
0.5≤Y/∑Ln≤0.95；0.01≤Gd/∑Ln≤0.5；0.001≤Tb/∑Ln≤0.05；0.001≤Lu/∑Ln≤0.05；0.001≤La/∑Ln≤0.05；0.01≤Ce/∑Ln≤0.1；0.001≤Dy/∑Ln≤0.05；0.0001≤Pr/∑Ln≤0.05；
Wherein, ∑ Ln=Y and/or Gd and/or Tb and/or Lu and/or La and/or Ce and/or Pr.
That below will explain element in the fluorescent material composition that adopts may act on the main ruthenium ion component of positively charged ion lattice.Y wherein
+ 3Ionic radius size τ
Y=0.97A, coordination K=8 is at ion Y
+ 3Around 8 other ions that distribute, relevant ion Y in the positively charged ion lattice
+ 3Can following ion La
+ 3, Gd
+ 3, Tb
+ 3, Lu
+ 3Replace its ionic radius size τ
La=1.06A, τ
Gd=0.98A, τ
Tb=0.89A, τ
Lu=0.86A is at ion La
+ 3Introducing can be relaxed garnet crystal lattice.
Attention is about adding Gd in the positively charged ion lattice
+ 3Ion, if in the calculating [Gd]=0.2 of traditional standard, for orange-yellow radiation and [Gd]＞0.4 for orange radiation.Someone points out, at fluorescent material proposed by the invention or employing Ce
+ 3And Dy
+ 3Two kinds, perhaps Ce
+ 3, Dy
+ 3, Pr
+ 3Three kinds are activated compositions, they each have special effect, ion Ce
+ 3At 5d
2Self produce the radiation 480～760nm in broadband, must quote ion Dy
+ 3Guaranteed ion Ce
+ 3The sensibilized of radiation for faint its regional extent of crooked spectrum λ=580nm occurring, is added ion Pr
+ 3, can produce the spectrum of a relative maximum wavelength λ=610nm.
Introduce ion Tb
+ 3With Lu
+ 3Its intracell electrostatic field of change that will be strong, and little size ion τ for example
LuThe maximum of=0.83A is filled, and has ensured the very electrostatic field of high-gradient, and has affected active ions Ce
+ 3, Dy
+ 3, Pr
+ 3Sensibilized.
The present invention adds [Tb at fluorescent material
+ 3The atomic fraction concentration of]=0.01, brightness has increased by 1% thereupon.Fluorescent material adds ion Lu
+ 3, find the displacement of excitation spectrum generation shortwave, move to λ=457nm from λ=465nm.
In anion lattice, introduce silicon ion Si
+ 4And iodide ion I
-1, aluminum ion Al
+ 3By silicon ion Si
+ 4Replace.In the increase of radiative process part, luminosity is increased.On the other hand, silicon ion Si
+ 4Change simultaneously inner lattice electrostatic field, make ion Ce here
+ 3Radiation wavelength increase.
Different valency is replaced, and adopts iodide ion I
-1Different valency is replaced O
-2, change its radiation spectrum symmetrical, strengthen in orange red radiation wavelength sub-band.
The present invention can introduce the not iodide ion of volume equally in fluoroscopic photographic developer, the displacement of 2～8nm occurs at wavelength.
Here point out not every iodide ion I in practical situation
-1Can hold, so in heat treatment process, I may be arranged
2Throw out.
The applicant once adopted following: be positioned at Si
+ 4Ion in, enter in the coordination polyhedron, in main ion composition, increase the introduction amount, perhaps increase gaseous product or solid-state reagent, for example: BaI
2Calculate the luminescent spectrum of all special radiation with this.
The fluorescent material composition that adopts in experiment is listed in the lower tabulation 1.
Table 1
| The fluorescent material component | Greatest irradiation spectrum, nm | Chromaticity coordinates x, y | λ 0.5 nm | Luminosity | |
| 1 | (Y 0.80Gd 0.15Tb 0.01Lu 0.01Ce 0.03) 3 Al 2(AlO 4) 3 | 560.8 | 0.3960 0.4536 | 119.8 | 23051.5 |
| 2 | (Y 0.75Gd 0.16Tb 0.01Lu 0.15Ce 0.029Dy 0.0 01) 3Al 2(Al 0.997Si 0.003O 3.997I 0.003) 4 | 562.4 | 0.3866 0.4382 | 121.6 | 22745 |
| 3 | (Y 0.70Gd 0.12Tb 0.05Lu 0.05La 0.03Ce 0.04 Dy 0.01) 3Al 2(Al 0.99Si 0.01O 3.99I 0.01) 3 | 568.7 | 0.4203 0.4600 | 120.4 | 26359 |
| 4 | (Y 0.70Gd 0.2Tb 0.01Lu 0.01La 0.04Ce 0.03D y 0.005Pr 0.005) 3Al 2(Al 0.97Si 0.03O 3.97I 0. 03) 3 | 609.8 | 0.4458 0.4231 | 127.6 | 20349 |
Under request in person in the lump with reference to Fig. 1～Fig. 4, wherein Fig. 1 a is the spectral distribution graph of the radiation spectrum of sample 1 in the table 1, Fig. 1 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 1 in the table 1; Fig. 2 a is the spectral distribution graph of the radiation spectrum of sample 2 in the table 1, and Fig. 2 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 2 in the table 1; Fig. 3 a is the spectral distribution graph of the radiation spectrum of sample 3 in the table 1, and Fig. 3 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 3 in the table 1; Fig. 4 a is the spectral distribution graph of the radiation spectrum of sample 4 in the table 1, and Fig. 4 b is the CIE1931 chromaticity diagram of the radiation spectrum of sample 4 in the table 1.
Please refer to Fig. 5, it shows the configuration diagram according to the white light emitting diode of iodide garnet phosphor powder made of the present invention.As shown in the figure, wherein 1 is an InGaN heterojunction semiconductor, and 2,3 are pin (being the leading-in end of electronics), and 4 is conic reflector.Form a luminescent conversion layer 5 on the top layer of heterojunction 1, its polymeric film is arranged in and is distributed in its fluorescent powder grain 6.In addition, on this luminescent conversion layer 5, further has a spherical cap 8, to reinforce the convergence reflex mirror.In addition, internal illumination conversion layer 5 and 8 transparent of spherical cap are filled with resin 7.
Please refer to Fig. 6, it is the schematic diagram of the X ray of sample 3 in the table 1.As shown in the figure, the migration on spectrum DOPOH 2 is X ray U=45 electron-volt (equipment obtains the filtration from the Ni paper tinsel, and X ray is monochromaticity more).
As Fig. 2 relatively in minimum iodide ion I
-1Maximum spectrum lambda=562nm of forming of component (＜0.005 atomic fraction concentration).By I
-1The growth of≤0.01 atomic fraction concentration transits to maximum spectral value to λ=568nm, and spectral hand is to λ simultaneously
0.5=124.5nm, last in synthesis gas the ionic concn of product increase and original raw material in do not cause that radiation spectrum changes, (at positively charged ion lattice Gd
+ 3, Tb
+ 3And Lu
+ 3).The maximum luminous radiation of spectrum that demonstrates iodide garnet provided by the present invention battalion light powder was not described in previous special novel material.Two combinations of iodide garnet phosphor powder of the present invention are arranged in: 1. at the O of anion lattice
-2By garnet iodide ion I in the lattice
-1Substitute; 2. iodide ion I
-1Concentration and silicon ion Si
+ 4Concentration identical.
Add in the fluorescent material provided by the present invention and introduce silicon ion, its difference is to have cubic system garnet framework and have parameter a 〉=12.08A.
Lattice parameter really fixes in the garnet phosphor powder proposed by the invention modulation (as shown in Figure 6) and points out, arrange framework at main garnet crystal, its activation and chemical formula are:
Y
2O
3+I
2→2YOI+1/2O
2 (1)
Its oxidation is set in cold putting in the crucible, the reaction process that wherein produces, and similar process uses aluminium hydroxide, its chemical equation in above-mentioned chemical formula (1):
Al(OH)
3+I
2→AlOI+HI+H
2O+1/2O
2 (2)
In addition, can be connected with the YOI of rare earth ion for iodine aluminium oxide Al OI, the iodide ion that reason is to produce is in the lattice of fluorescent material proposed by the invention.The present invention uses the data of not obtaining relevant aluminium hydroxide in the heat treated reference, still, and for AlI
3, ℃ lower molecule does not decompose in this temperature T=382.5.
The present invention also points out the iodo-silicate fluorescent powder with garnet framework proposed by the invention: 1. its maximum spectrum lambda that produces=560～568nm; 2. for the wide radiation lambda of half-wave that increases spectrum
0.5=119～120.6nm; 3. obviously unequal in the radiation of orange red radiant light spectral coverage.
Here to point out, when concentration x=0.03 atomic fraction concentration, at " balance " I
-1Ion and Si
+ 4Silicon ion makes that the luminosity of fluorescent material is substantial to have promoted 10%.Such brightness, the chances are active ions Ce
+ 3Be subject to undersized silicon ion Si
+ 4Impact.
The component of all fluorescent material sample evidence positively charged ion lattices conforms to the component of formula of the present invention, and main purpose is to reduce Gd in the fluorescent material
+ 3The introducing amount, its luminosity increases.In the fluorescent material fabric arrangement of standard, usually increase the concentration of Gd, luminosity can descend.
In the process of invention, emphasize that fluorescent material proposed by the invention also has a special performance, be included in the thin loose particle component and between sintering.Neutrality line diameter dimension for standard garnet phosphor powder particle is d
50=4 microns, increasing numerical value d
90In the time of=16～18 microns, analyze fluorescent material proposed by the invention and lack the macrobead sintering.
All light-emitting particles all have disciform form, lack faceted pebble simultaneously in the form of particle, and the marginal layer of particle does not increase mutual bonding layer.
The advantage of fluorescent material proposed by the invention is, solid-phase synthesis and synthesizing rare-earth furnace charge is characterized in that: introduce silicon oxide in the reagent composition, adding man-hour and add the concentration to 0.1% of reducing gas, it is 1280～1480 ℃ that furnace temperature is set, and the time length is 2～20 hours.
With method processing proposed by the invention, with HNO
3With H
2O was according to 1: 1 ratio (HNO
3: H
2O=1: 1) process.The particle of fluorescent material forms with silicate ZnOSiO in the process of processing
2Film for the basis.
The numbering of synthetizing phosphor powder and record by experiment the characteristic of all photoptometrys (photometry) and spectrum.In all parameters as described in Table 1, the difference of its fluorescent material can be set up the cold white tone with standard about the employing of bright-Yellow luminous material, the photodiode that warm white is transferred.
In the Organization Chart of the photodiode of Fig. 5, being derived from InGaN heterojunction semiconductor 1 is positioned at take crystal cartridge as the basis, point out that its luminescent conversion layer 5 has two Component Systems, inorganic fluorescent powder 6 is mixed mutually with organic polymer (figure is expression not), the difference of the luminescent conversion layer 5 that proposes for semiconductor light-emitting-diode, even thickness on each plane and the side is 80～200 microns.This working method with specialty will combine with fluorescent material 6, and the faceted pebble of whole radiation of heterojunction 1 and end face cladding thickness are even, are covered by the formed polymeric layer of inorganic fluorescent powder 6 and organic polymer.
In the process of the present invention experiment, it is 8: 92 to 75: 25 for quantity composition and the proportion of composing between the organic polymer of fluorescent powder grain 6.If the quantity of fluorescent material is less than 8% of indication concentration, then luminescent conversion layer 5 will be very transparent, producing a large amount of blue lights penetrates, on the other hand, if more than 75%, luminescent conversion layer 5 will be very thin to fluorescent powder grain 6 so in luminescent conversion layer 5, can be colorific inhomogeneous, must follow optical laws, wherein the optimum value of fluorescent material 6 quality in the luminescent conversion layer 5 is 18～32%.
Photodiode as shown in Figure 6, the numerical value that obtains is from the spectral radiance analyser of three looks (Sensing) company.The luminous intensity numerical value of the axial heart of photodiode is promoted to 100cd, and two angle of releases are 2 θ=60 °, and colour temperature is T=4800-5600K, is positioned at the semiconductor cooling white light and the warm white instrument that reach the standard of obtaining.
Record the logical measurement of whole light in spherical cap 8, optical throughput is promoted to F＞110 lumens, and for the equipment of power W=1 watt, above-mentioned photodiode with very high integrated parameter-its luminous efficiency is promoted to η＞100 lumens/watt.
Although the present invention discloses as above with preferred embodiment; so it is not to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; all can do a little and change and retouching, so protection scope of the present invention should be as the criterion with appending claims.
Claims (9)
1. iodide garnet phosphor powder, its be rare earth oxide element take the garnet framework as matrix, it is characterized in that: in this phosphor material powder, add and introduce iodide ion I
-1And silicon ion Si
+ 4, mutual compensate for electronic forms following chemometric equation: (∑ Ln) in the anion lattice
3Al
2(Al
1-xSi
xO
4-xI
x)
3, wherein ∑ Ln=Y and/or Gd and/or Tb and/or Lu and/or La and/or Ce and/or Pr and/or Dy, 0.0001＜x≤0.10; This fluorescent material radiation can produce the long wave displacement under the exciting of an InGaN heterojunction semiconductor.
2. iodide garnet phosphor powder according to claim 1, wherein said long wave displacement is Δ 〉=25nm.
3. iodide garnet phosphor powder according to claim 1, wherein as follows at the component of anion lattice rare earth elements ion:
0.5≤Y/∑Ln≤0.95；0.01≤Gd/∑Ln≤0.5；0.001≤Tb/∑Ln≤0.05；0.001≤Lu/∑Ln≤0.05；0.001≤La/∑Ln≤0.05；0.01≤Ce/∑Ln≤0.1；0.001≤Dy/∑Ln≤0.05；0.0001≤Pr/∑Ln≤0.05。
4. iodide garnet phosphor powder according to claim 1, wherein said fluorescent material has garnet cubic crystal framework, increases iodide ion I in its anion lattice
-1And silicon ion Si
+ 4Concentration, lattice parameter then can increase,
5. the preparation method of an iodide garnet phosphor powder, it is adding SiO for the preparation of iodide garnet phosphor powder as claimed in claim 1
2Heat treatment after the extremely initial rare earth reagent when heat treatment, is introduced iodide composition gas in addition in reducing gas.
6. white light emitting diode, it is as matrix take heterojunction semiconductor InGaN, and scribble a luminescent conversion layer, this luminescent conversion layer is distributed on this heterojunction radiating surface and the faceted pebble, and be added with fluorescent material as claimed in claim 1 in this luminescent conversion layer, it is characterized in that: the variation in thickness scope in this luminescent conversion layer is 80～200 microns, and even thickness.
7. white light emitting diode according to claim 6, wherein this luminescent conversion layer is comprised of silicate polymer and fluorescent material as claimed in claim 1, and its relationship between quality ratio is 92: 8～25: 75.
8. white light emitting diode according to claim 6 is the W=1 watt-hour in the supply exciting power wherein, ° angle, 2 θ=60, and its luminous intensity is 1＞30cd, colour temperature T＞4500K.
9. white light emitting diode according to claim 6 wherein is 1 watt diode for power, its optical throughput F＞110 lumens, light transmittance efficiency η＞100 lumens/watt.
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