CN101880529A - Wavelength conversion fluorescent material for halogen co-activated gallium aluminate white LED - Google Patents

Abstract

The invention provides a wavelength conversion fluorescent material for a halogen co-activated gallium aluminate white LED with high-efficiency coloring and photodegradation resistance. The material is characterized in that: the material has a general formula of G(3 a)Mb/2N5O12-b:Rea, Xb, wherein R is at least one of oxide, hydrate, oxalate and carbonate of La, Y, Lu, Gd, Tb, Nd and Ho elements; M is at least one of oxide, hydrate, oxalate and carbonate of Ca, Mg, Ba, Sr and Zn elements; N is at least one of oxide, hydrate, oxalate and carbonate of B, Al, Ga and In elements; Re is at least one of oxide, hydrate, oxalate and carbonate of Ce, Dy, Pr, Eu, Tm, Er, Sm, Yb and Sc elements; X is at least one of AlF3, CaF2, MgF2, BaF2, BaCl2, SrF2, SrCl2 and ZnCl2 containing F and Cl; and a is more than or equal to 0.001 and less than or equal to 0.5, and b is more than or equal to 0.01 and less than or equal to 1.

Description

A kind of halogen co-activated gallium aluminate white LED Wavelength conversion fluorescent material

Technical field

The present invention relates to a kind of halogen co-activated gallium aluminate white LED Wavelength conversion fluorescent material, it is to use on the blue light emitting chip forms white light-emitting diodes, can send the fluorescent material of white light by the wavelength Conversion combination, characteristics with the anti-light decay of efficient colour developing belong to the semiconductor illuminating light source field.

Background technology

Semiconductor illuminating light source has distinguishing features such as long lifetime, energy-saving and environmental protection, microminiaturization as new and effective solid light source, be described as 21 century novel illumination light source.Under the background of global energy shortage, white light LEDs gets most of the attention in illumination market.

It is Y that the patent of invention that Ri Ya chemical company in 1997 proposes US5998925 to United States Patent Office (USPO) discloses a kind of chemical formula₃Al₅O₁₂: Ce³⁺(YAG), also claim yttrium aluminum garnet, mix into white light LEDs with the iii-nitride light emitting devices of its research and development, this fluorescent material absorbs 450～470nm wavelength blue light, excites to produce 550～560nm wavelength gold-tinted, can produce white light behind the gold-tinted mixed light of remaining blue light and conversion, the synthetic white light LEDs has the advantages that cost is low, efficient is high, main drawback is that color developing is relatively poor, and the thickness dialogue influence of light of coating is bigger, lack of homogeneity.

It is Tb that U.S. Pat 6669866 has proposed chemical formula₃Al₅O₁₂: Ce³⁺(being called for short TAG), claim that also the terbium aluminium garnet is a fluorescent material, shortcoming is the cost height, and terbium costs an arm and a leg, and brightness is also poor than YAG.

Chinese patent 0213094913 proposes a kind of chemical formula: R_{(3 x y)}M₅O₁₂: Ce_x, R '_yWherein: R is Y, Gd, and Lu, Sc, La, one or more of Sm, M are B, Al, Ga, In, P, Ge, one or more of Zn, R ' they can be Tb, Eu, Dy, Pr, one or more of Mn.This fluorescent material is with respect to aforementioned Y₃Al₅O₁₂: Ce³⁺(YAG) the fluorescent material color developing improves, but the blue light efficiency of conversion of fluorescent material less than the former height, brightness is on the low side.

U.S. Pat 6809347 discloses a kind of fluorescent material chemical formula: (2-x-y) SrOx (Ba, Ca) O (1-a-b-c-d) SiO₂AP2O5 bAl₂O₃CB₂O₃DGcO₂: yEu²⁺(0.01≤x＜1.6; 0＜y＜0.5; X+y≤1.6; 0≤a, b, c, d＜0.5), use be the alkaline earths silicate that contains europium, Sr₂SiO₄Or Ba₂SiO₄For parent carries out the replacement of P, Al, B or Ge to Sr or Ba, this fluorescent material also is to use blue light to do and excites, and tangerine partially on photochromic, colour rendering index is up to 82.But brightness is lower, and white light is nature not.

U.S. Pat 20060027781 discloses a kind of fluorescent material chemical formula: A₂SiO₄: Eu²⁺, D (A=Sr, Ca, Mg, Zn, Cd, D=0.1～0.2mol %F, Cl, Br, I, P, S, N).This fluorescent material color developing is good, the light efficiency height also can be produced low color temperature white light, and shortcoming is that particle is thick, the easy moisture absorption, need two kinds of powder to carry out physical mixed, should not mix, easily layering, be unsuitable for a glue, bloom, green powder brightness is on the low side than YAG, contains heavy metal Cd in the rouge and powder, does not meet environmental requirement.

Summary of the invention

The shortcoming that the present invention exists at prior art just, it has high brightness with Wavelength conversion fluorescent material to propose the anti-light decay white light LEDs of the efficient colour developing of novel halogen co-activated gallium aluminate, and high-color rendering, low cost are anti-aging, the characteristics of anti-light decay.It is characterized by by following general formula: R_(3-a)M_B/2N₅O_12-b: Re_a, X_bThe fluorescent material of forming, wherein R is for being selected from La, Y, Lu, Gd, Tb, Nd, more than at least a in the oxide compound of Ho element or oxyhydroxide or oxalate or the carbonate, M is for being selected from Ca, Mg, Ba, Sr, more than at least a in the fluorochemical of Zn element and/or the muriate, N is B, Al, Ga, more than at least a in the oxide compound of In element or oxyhydroxide or oxalate or carbonate or the fluorochemical, Re is that activator is for being selected from Ce, Dy, Pr, Eu, Tm, Er, Sm, Yb, the oxide compound of Sc element, oxyhydroxide, more than at least a in oxalate or the carbonate, X is that coactivator contains F for being selected from, the AlF of Cl element₃, CaF₂, MgF₂, BaF₂, BaCl₂, SrF₂, SrCl₂, ZnCl₂In at least a more than, and 0.001≤a≤0.5,0.01≤b≤1, simultaneously, AlF₃, CaF₂, MgF₂, BaF₂, BaCl₂, SrF₂, SrCl₂, ZnCl₂Also play the effect of fusing assistant.

White light LEDs Wavelength conversion fluorescent material of the present invention, it is characterized by can by 250nm～490nm by UV-light to blue-light excited.

White light LEDs Wavelength conversion fluorescent material of the present invention is characterized by the visible light emitted spectrum and is 450nm～700nm, and its peak value is at 530nm～610nm.

White light LEDs Wavelength conversion fluorescent material of the present invention is characterized by and can use general formula (Y_1-j, Gd_j)_3-aBa_B/2(Al_1-k, Ga_k)₅O_12-b: (Ce_1-iPr_i)_a, (F_1-zCl_z)_bExpression, wherein 0.001≤a≤0.5,0.01≤b≤1,0.001≤j≤0.9,0.01≤k≤0.5,0.001≤i≤0.1,0.1≤z≤0.5.Here, Pr is coactivator and in the orange red district of 610nm emission peak is arranged, form bimodal with Ce at the yellow light area peak of 530nm～583nm, in with a kind of matrix, produce the binary colour light emitting like this, luminous with the blue light composition three-primary colours of blue chip, improved colour rendering index, two primary colors are in same matrix simultaneously, guaranteed the homogeneity of color, consistence and stability.

White light LEDs Wavelength conversion fluorescent material of the present invention, it is characterized by X is coactivator F and Cl, and when 0.1≤z≤0.125, along with reducing of z value, its emmission spectrum moves to the shortwave direction, when 0.125≤z≤0.5, along with the increase of z value, its emmission spectrum moves to the long wave direction, emission peak is positioned at 530nm～610nm, and in 0.01≤b≤1 interval, along with the increase of b value, luminous intensity increases.

White light LEDs Wavelength conversion fluorescent material of the present invention, it is characterized by by changing Y, the ratio emission spectra peak of Gd is moved, when j increases in 0.001≤j≤0.9 interval gradually, the emmission spectrum peak value moves to the long wave direction, otherwise, then moving to the shortwave direction, emission peak is positioned at 530nm～610nm.

White light LEDs Wavelength conversion fluorescent material of the present invention, it is characterized by by changing Al, the ratio emission spectra peak of Ga is moved, when k increases in 0.01≤k≤0.5 interval gradually, the emmission spectrum peak value moves to the shortwave direction, otherwise, then moving to the long wave direction, emission peak is positioned at 530nm～610nm.

The white light LEDs of the present invention preparation method of Wavelength conversion fluorescent material, it is characterized by mole proportioning weighing, mix, under the reducing atmosphere of nitrogen, hydrogen gas mixture by the structural formula regulation, 1350～1500 ℃ ofsintering temperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.

The white light LEDs of the present invention preparation method of Wavelength conversion fluorescent material, it is characterized by and can selecting carbonate or oxalate for use is the ultra-fine fluorescent material of feedstock production, because carbonate or oxalate decomposes can make the particle that burns till littler; But because the carbon that carbonate and oxalate can be reduced into simple substance under reducing atmosphere produces Prevent Carbon Contamination, so sintering process will be carried out in two steps, earlier 1000 ℃ of oxidizing atmosphere sintering 2 hours, cooling, 1350～1500 ℃ of sintering 3～5 hours, cooling obtained mean particle size D again₅₀It is the loose powder of 2～4 μ m.

White light LEDs of the present invention is characterized by the powder La that obtains with the preparation method of Wavelength conversion fluorescent material₂O₃Carrying out coating handles, performance with anti-aging anti-light decay, lanthanum nitrate hexahydrate with 0.1% is handled fluorescent powder particulate surface, add the ammoniacal liquor neutralization again, at the glued membrane of 1～2 nanometer of particle surface formation, after 130～150 ℃ of oven dry 10～16 hours, just form the coating of anti-aging anti-light decay, the temperature of the anti-150 ℃ of temperature of the fluorescent material that obtains is aging, nondiscoloration, sad subtracting not, and stability is strong.

White light LEDs Wavelength conversion fluorescent material of the present invention, it is characterized by with Resins, epoxy or silicone resin and make on the chip that coating is coated in 410nm～490nm, and get up with transparent Resins, epoxy or silicone encapsulation, the blue-light excited fluorescent material that the chip energising is sent produces the gold-tinted of peak value at 530nm～610nm, becomes white light source with the blue light that part transmits again.

Description of drawings

Accompanying drawing 1 explanation fluorescent material of the present invention is by changing Y, and the ratio emission spectra peak of Gd is moved, and when j increased in 0.001≤j≤0.9 interval gradually, the emmission spectrum peak value moved to the shortwave direction, otherwise, then move to the long wave direction.

Accompanying drawing 2 explanations fluorescent material of the present invention is by changing Al, and the ratio emission spectra peak of Ga is moved, and when k increased in 0.01≤k≤0.5 interval gradually, the emmission spectrum peak value moved to the shortwave direction, otherwise, then move to the long wave direction.

Accompanying drawing 3 contrast YAG:Ce³⁺Illustrate that fluorescent material Pr of the present invention is coactivator and in the orange red district of 610nm emission peak is arranged, form bimodal with Ce at the yellow light area peak of 530nm～583nm, in with a kind of matrix, produce the binary colour light emitting like this, form three primary colors with the blue light that excites, and YAG:Ce³⁺Have only two primary colors.

The X that is characterized as of accompanying drawing 4 explanation fluorescent material of the present invention is coactivator F and Cl, and when 0.1≤z≤0.125, along with reducing of z value, its emmission spectrum moves to the shortwave direction, when 0.125≤z≤0.5, along with the increase of z value, its emmission spectrum moves to the long wave direction.

The X that is characterized as of accompanyingdrawing 5 explanation fluorescent material of the present invention is coactivator F and Cl, and when 0.01≤b≤1, along with the increase of b value, its emission peak enhancing, brightness is the highest when b=0.4.

Embodiment

For fluorescent material of the present invention and preparation method are described, enumerate following examples and describe, but the present invention are subjected to the restriction of following practical range.

Embodiment 1:(Y_0.95Gd_0.05)_2.9Ba_0.1(Al_0.9Ga_0.1)₅O_11.8: (Ce_0.94Pr_0.06)_0.1(F_0.9Cl_0.1)_0.2Preparation

Get the reagent material by following weighing balance

Y₂O₃(5N) 1.3775mol

Gd₂O₃(4N) 0.145mol

Al(OH)₃ 4.5mol

Ga₂O₃(4N) 0.25mol

CeO2(4N) 0.094mol

Pr₆O₁₁(4N) 0.001mol

AlF₃(4N) 0.03mol

BaF2(4N) 0.05mol

BaCl2(4N) 0.01mol

After grinding mixing, pack above-mentioned material into the high purity aluminium oxide crucible under the atmosphere of hydrogen nitrogen mixed gas (75% volume ratio), 1350～1500 ℃ of sinteringtemperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.Clean with rare nitric acid, be washed to neutrality, add 0.1% lanthanum nitrate and add in the ammoniacal liquor again and the suction filtration oven dry obtains the powder of coating.Under 460nm is blue-light excited, send the 567nm gold-tinted, produce strong glow peak at the 610nm place.

Embodiment 2:(Y_0.25Gd_0.75)_2.9Ba_0.1(Al_0.9Ga_0.1)₅O_11.8: (Ce_0.94Pr_0.06)_0.1(F_0.9Cl_0.1)_0.2Preparation

Get the reagent material by following weighing balance

Y₂O₃(5N) 0.3625mol

Gd₂O₃(4N) 1.0875mol

Al(OH)₃(4N) 4.5mol

Ga₂O₃(4N) 0.25mol

CeO2(4N) 0.094mol

Pr₆O₁₁(4N) 0.001mol

AlF₃(4N) 0.03mol

BaF2(4N) 0.05mol

BaCl2(4N) 0.01mol

After grinding mixing, pack above-mentioned material into the high purity aluminium oxide crucible under the atmosphere of hydrogen nitrogen mixed gas (75% volume ratio), 1350～1500 ℃ of sinteringtemperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.Clean with rare nitric acid, be washed to neutrality, add 0.1% lanthanum nitrate and add in the ammoniacal liquor again and the suction filtration oven dry obtains the powder of coating.Compare withembodiment 1, under 460nm is blue-light excited, send 578nm yellow orange light, produce strong glow peak at the 610nm place.

Embodiment 3:(Y_0.95Gd_0.05)₂₉Ba_0.1(Al_0.6Ga_0.4)₅O_11.8: (Ce_0.94Pr_0.06)_0.1(F_0.9Cl_0.1)_0.2Preparation

Get the reagent material by following weighing balance

Y₂O₃(5N) 1.3775mol

Gd₂O₃(4N) 0.145mol

Al(OH)₃ 3.0mol

Ga₂O₃(4N) 1.0mol

CeO2(4N) 0.094mol

Pr₆O₁₁(4N) 0.001mol

AlF₃(4N) 0.03mol

BaF2(4N) 0.05mol

BaCl2(4N) 0.01mol

After grinding mixing, pack above-mentioned material into the high purity aluminium oxide crucible under the atmosphere of hydrogen nitrogen mixed gas (75% volume ratio), 1350～1500 ℃ ofsintering temperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.Clean with rare nitric acid, be washed to neutrality, add 0.1% lanthanum nitrate and add in the ammoniacal liquor again and 130～150 ℃ of oven dry of suction filtration obtain the powder of coating.Compare withembodiment 1, under 460nm is blue-light excited, send the 538nm yellow green light, produce strong glow peak at the 610nm place.

Embodiment 4:(Y_0.95Gd_0.05)_2.9Ba_0.1(Al_0.9Ga_0.1)₅O_11.8: (Ce_0.94Pr_0.06)_0.1(F_0.6Cl_0.4)_0.2Preparation

Get the reagent material by following weighing balance

Y₂O₃(5N) 1.3775mol

Gd₂O₃(4N) 0.145mol

Al(OH)₃ 4.5mol

Ga₂O₃(4N) 0.25mol

CeO2(4N) 0.094mol

Pr₆O₁₁(4N) 0.001mol

AlF₃(4N) 0.015mol

BaF2(4N) 0.04mol

BaCl2(4N) 0.04mol

After grinding mixing, pack above-mentioned material into the high purity aluminium oxide crucible under the atmosphere of hydrogen nitrogen mixed gas (75% volume ratio), 1350～1500 ℃ ofsintering temperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.Clean with rare nitric acid, be washed to neutrality, add 0.1% lanthanum nitrate and add in the ammoniacal liquor again and 130～150 ℃ of oven dry of suction filtration obtain the powder of coating.Compare withembodiment 1, under 460nm is blue-light excited, send the 571nm gold-tinted, produce strong glow peak at the 610nm place.

Embodiment 5:(Y_0.95Gd_0.05)_2.9Ba_0.1(Al_0.9Ga_0.1)₅O_11.8: (Ce_0.94Pr_0.06)_0.1(F_0.75Cl_0.25)_0.2Preparation

Get the reagent material by following weighing balance

Y₂O₃(5N) 1.3775mol

Gd₂O₃(4N) 0.145mol

Al(OH)₃ 4.5mol

Ga₂O₃(4N) 0.25mol

CeO2(4N) 0.094mol

Pr₆O₁₁(4N) 0.001mol

AlF₃(4N) 0.03mol

BaF2(4N) 0.03mol

BaCl2(4N) 0.025mol

After grinding mixing, pack above-mentioned material into the high purity aluminium oxide crucible under the atmosphere of hydrogen nitrogen mixed gas (75% volume ratio), 1350～1500 ℃ ofsintering temperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.Clean with rare nitric acid, be washed to neutrality, add 0.1% lanthanum nitrate and add in the ammoniacal liquor again and 130～150 ℃ of oven dry of suction filtration obtain the powder of coating.Under 460nm is blue-light excited, send the 570nm gold-tinted, produce strong glow peak at the 610nm place.

Embodiment 6:(Y_0.95Gd_0.05)_2.9Ba_0.2(Al_0.9Ga_0.1)₅O_11.6: (Ce_0.94Pr_0.06)_0.1(F_0.75Cl_0.25)_0.4Preparation

Get the reagent material by following weighing balance

Y₂O₃(5N) 1.3775mol

Gd₂O₃(4N) 0.145mol

Al(OH)₃ 4.5mol

Ga₂O₃(4N) 0.25mol

CeO2(4N) 0.094mol

Pr₆O₁₁(4N) 0.001mol

AlF₃(4N) 0.06mol

BaF2(4N) 0.06mol

BaCl2(4N) 0.05mol

After grinding mixing, pack above-mentioned material into the high purity aluminium oxide crucible under the atmosphere of hydrogen nitrogen mixed gas (75% volume ratio), 1350～1500 ℃ ofsintering temperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.Clean with rare nitric acid, be washed to neutrality, add 0.1% lanthanum nitrate and add in the ammoniacal liquor again and 130～150 ℃ of oven dry of suction filtration obtain the powder of coating.Under 460nm is blue-light excited, send the 570nm gold-tinted, produce strong glow peak at the 610nm place, luminosity is 110% ofembodiment 5.

Embodiment 7: adopt oxalate preparation (Y_0.95Gd_0.05)_2.9Ba_0.1(Al_0.9Ga_0.1)₅O_11.8: (Ce_0.94Pr_0.06)_0.1(F_0.9Cl_0.1)_0.2

Get the reagent material by following weighing balance

Y₂(C₂O₄)₃(5N) 1.3775mol

Gd₂(C₂O₄)₃(4N) 0.145mol

Al(OH)₃ 4.5mol

Ga₂(C₂O₄)₃(4N) 0.25mol

Ce(C₂O₄)₂(4N) 0.094mol

Pr₆(C₂O₄)₁₁(4N) 0.001mol

AlF₃(4N) 0.03mol

BaF2(4N) 0.05mol

BaCl2(4N) 0.01mol

Accurate weighing Y₂(C₂O₄)₃(5N) 1.3775mol, Gd₂(C₂O₄)₃(4N) 0.145mol, Al (OH)₃4.5mol, Ga₂(C₂O₄)₃(4N) 0.25mol, Ce (C₂O₄)₂(4N) 0.094mol, Pr₆(C₂O₄)₁₁(4N) after grinding mixing, oxalate is decomposed in the high purity aluminium oxide crucible roasting 2～3 hours under 800 ℃～1000 ℃ oxidizing atmosphere of packing into to 0.001mol with above-mentioned material, and the said mixture material is taken out in cooling, adds AlF again₃(4N) 0.03mol, BaF2 (4N) 0.05mol, BaCl2 (4N) 0.01mol ground and mixed are even, the high purity aluminium oxide crucible pack under the atmosphere of hydrogen nitrogen mixed gas (75% volume ratio), 1350～1500 ℃ of sintering temperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.Clean with rare nitric acid, be washed to neutrality, add 0.1% lanthanum nitrate and add in the ammoniacal liquor again and 130～150 ℃ of oven dry of suction filtration obtain the powder of coating.Under 460nm is blue-light excited, send the 567nm gold-tinted, produce strong glow peak at the 610nm place.

Embodiment 8: the phosphor for white light LED to the foregoingdescription 1～7 adopts the 1w high-power chip, carries out package experiment with Resins, epoxy in the ratio of 16% (weight), and test result is as follows:

Data show, use La₂O₃Carry out coating and handle, the fluorescent material that obtains is ageing-resistant, nondiscoloration, decay hardly, and stability is strong, the ultra-fine mill of exempting from of the fluorescent material that oxalate is made, stability is better.

Claims (10)

1. a halogen co-activated gallium aluminate white LED Wavelength conversion fluorescent material is characterized by by following general formula: R_(3-a)M_B/2N₅O_12-b: Re_a, X_bThe fluorescent material of forming, wherein R is for being selected from La, Y, Lu, Gd, Tb, Nd, more than at least a in the oxide compound of Ho element or oxyhydroxide or oxalate or the carbonate, M is for being selected from Ca, Mg, Ba, Sr, more than at least a in the fluorochemical of Zn element and/or the muriate, N is B, Al, Ga, more than at least a in the oxide compound of In element or oxyhydroxide or oxalate or carbonate or the fluorochemical, Re is that activator is for being selected from Ce, Dy, Pr, Eu, Tm, Er, Sm, Yb, more than at least a in the oxide compound of Sc element or oxyhydroxide or oxalate or the carbonate, X is that coactivator contains F for being selected from, the AlF of Cl element₃, CaF₂, MgF₂, BaF₂, BaCl₂, SrF₂, SrCl₂, ZnCl₂In at least a more than, simultaneously, AlF₃, CaF₂, MgF₂, BaF₂, BaCl₂, SrF₂, SrCl₂, ZnCl₂Also play the effect of fusing assistant, and 0.001≤a≤0.5,0.01≤b≤1.

2. white light LEDs Wavelength conversion fluorescent material according to claim 1 is characterized by and can use general formula (Y_1-j, Gd_j)_3-aBa_B/2(Al_1-k, Ga_k)₅O_12-b: (Ce_1-iPr_i)_a, (F_1-zCl_z)_bExpression, wherein 0.001≤a≤0.5,0.01≤b≤1,0.001≤j≤0.9,0.01≤k≤0.5,0.001≤i≤0.1,0.1≤z≤0.5.

3. according to claim 1,4 described white light LEDs Wavelength conversion fluorescent materials, it is characterized by Pr and be coactivator and emission peak is arranged in the orange red district of 610nm, form bimodal with Ce at the yellow light area peak of 530nm～583nm.

4. white light LEDs Wavelength conversion fluorescent material according to claim 1, it is characterized by X is coactivator F and Cl, and when 0.1≤z≤0.125, along with reducing of z value, its emmission spectrum moves to the shortwave direction, when 0.125≤z≤0.5, along with the increase of z value, its emmission spectrum moves to the long wave direction, emission peak is positioned at 530nm～610nm, and in 0.01≤b≤1 interval, along with the increase of b value, luminous intensity increases.

5. according to claim 1,4 described white light LEDs Wavelength conversion fluorescent materials, it is characterized by by changing Y, the ratio emission spectra peak of Gd is moved, when j increases in 0.001≤j≤0.9 interval gradually, the emmission spectrum peak value moves to the long wave direction, otherwise, then moving to the shortwave direction, emission peak is positioned at 530nm～610nm.

6. according to claim 1,4 described white light LEDs Wavelength conversion fluorescent materials, it is characterized by by changing Al, the ratio emission spectra peak of Ga is moved, when k increases in 0.01≤k≤0.5 interval gradually, the emmission spectrum peak value moves to the shortwave direction, otherwise, then moving to the long wave direction, emission peak is positioned at 530nm～610nm.

7. the white light LEDs according to claim 1 preparation method of Wavelength conversion fluorescent material, it is characterized by mole proportioning weighing, mix, under the reducing atmosphere of nitrogen, hydrogen gas mixture by the structural formula regulation, 1350～1500 ℃ of sintering temperatures 3～5 hours, cooling obtains mean particle size D₅₀It is the loose powder of 4～7 μ m.

8. the white light LEDs according to claim 1 preparation method of Wavelength conversion fluorescent material, sintering process will be carried out in two steps when it is characterized by the raw material of selecting for use and being carbonate or oxalate, earlier 1000 ℃ of oxidizing atmosphere sintering 2 hours, cooling, 1350～1500 ℃ of sintering 3～5 hours, cooling obtained mean particle size D again₅₀It is the loose powder of 3～5 μ m.

9. white light LEDs according to claim 1 is characterized by the powder La that obtains with the preparation method of Wavelength conversion fluorescent material₂O₃Carry out coating and handle, have the performance of anti-aging anti-light decay.

10. white light LEDs Wavelength conversion fluorescent material according to claim 1, it is characterized by and to form white light LEDs, it constitutes with Resins, epoxy or silicone resin and makes on the chip that coating is coated in 410nm～490nm, and get up with transparent Resins, epoxy or silicone encapsulation, the blue-light excited fluorescent material that the chip energising is sent produces the gold-tinted of peak value at 530nm～610nm, becomes white light source with the blue light that part transmits again.

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