CN107880885B - Garnet type aluminosilicate phosphor, method of preparing the same, and light emitting device including the same - Google Patents
Garnet type aluminosilicate phosphor, method of preparing the same, and light emitting device including the same Download PDFInfo
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- 229910000323 aluminium silicate Inorganic materials 0.000 title claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 11
- 239000002223 garnet Substances 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 50
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 230000000875 corresponding effect Effects 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 238000009877 rendering Methods 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 9
- 238000000695 excitation spectrum Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- -1 rare earth ions Chemical class 0.000 description 8
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910018173 Al—Al Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910019064 Mg-Si Inorganic materials 0.000 description 3
- 229910019406 Mg—Si Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005090 crystal field Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910017113 AlSi2 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
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Abstract
Discloses garnet type aluminosilicate fluorescent powder, which has a chemical formula as follows: (Lu)1‑x‑yLnxCey)aMgbAlcSidOeWherein a is more than or equal to 1.8 and less than or equal to 2.2, b is more than or equal to 1.8 and less than or equal to 2.1, c is more than or equal to 1.8 and less than or equal to 2.2, d is more than or equal to 1.8 and less than or equal to 2.1, e is more than or equal to 11.8 and less than or equal to 12.2, Ln is one or a combination of more of Sc, Y, Gd and La according to any proportion, x is more than or equal to 0 and less than<y is less than or equal to 0.08. The fluorescent material prepared by the invention has a crystal structure of yttrium aluminum garnet, can be excited by light with the wavelength less than 520nm, and emits visible light with the peak value of 560nm to 590 nm. In addition, a preparation method of the fluorescent powder and a light-emitting device comprising the fluorescent powder are also disclosed.
Description
Technical Field
The invention belongs to the field of rare earth luminescent materials, relates to garnet type fluorescent powder, a preparation method thereof and a luminescent device comprising the same, and more particularly relates to garnet type fluorescent powder which can be strongly excited by purple light and blue light to generate relative YAG to Ce3+A garnet-type aluminosilicate phosphor of yellow-orange light having a red-shifted emission peak, a method of preparing the same, and a light emitting device including the same.
Background
In recent years, white light LEDs have attracted attention and research because of their incomparable advantages over other conventional light sources, such as high energy efficiency, low operating voltage, long lifetime, low pollution, high stability, etc. The most mature white light LED preparation technology in the prior art is a phosphor coating light conversion method, so that the performance of the phosphor plays an important role in the white light LED performance.
Ce coating blue LED chip3+Yellow powder is widely used because of its advantages of high efficiency, simple preparation, low cost, etc. However, its emission in the red region is insufficient, resulting in a low color rendering index (Ra. ltoreq. 78)And the color temperature is higher (CCT is larger than or equal to 4500K), so that the requirement of high-quality illumination cannot be met. In order to produce warm white LED with low color temperature and high color rendering index, Ce is generally adopted as YAG3+Yellow phosphor is mixed with, for example, (Sr, Ca) S: Eu2+、CaAlSiN3:Eu2+The red phosphor powder with sulfide or nitride matrix capable of being excited by blue light can compensate YAG to Ce3+However, these red powders have respective problems, which makes them not widely applicable, for example: sulfide has poor stability and causes sulfur pollution to the environment; the synthesis conditions of the nitride are harsh, and the preparation cost is high. Therefore, the development of the novel efficient yellow orange fluorescent powder suitable for the white light LED has extremely important significance.
Because of the strong crystal field strength and the simple preparation process, the garnet structural matrix is greatly valued in the process of exploring and synthesizing the novel yellow-orange fluorescent powder. In 2006, Setlur et al synthesized a novel garnet structure Lu with an emission main peak around 605nm by a solid phase method2CaMg2Si3O12:Ce3+A phosphor (non-patent document 1). After being packaged with a blue LED chip, the color temperature is reduced, however, the color rendering index is low (76), and the quantum efficiency of the fluorescent powder is not high (about 60%). In addition, Katelnikovas et al reported Ce at YAG3+On the basis of the method, a novel Y with the emission main peak of about 600nm is synthesized by a method of replacing Al-Al with Mg-Si3Mg2AlSi2O12:Ce3+Phosphor (non-patent document 2) capable of compensating for YAG: Ce3+The red light region is insufficient, but the thermal quenching performance is relatively poor, and the practical application is not good. Further, pany et al are at YAG to Ce3+On the basis of the synthesis method, novel orange Y is synthesized by replacing Al-Al with Mg-Si and replacing Y-Al with Mg-Si2Mg2Al2Si2O12:Ce3+The phosphor (non-patent document 3) has a drawback that although the color rendering index is improved, the thermal quenching performance is relatively poor and the quantum efficiency is low. To solve the problem of improving the thermal quenching performance, Wangyihua et al have LuAG: Ce3+On the basis, the Lu with higher thermal quenching performance than commercial yellow powder is synthesized by replacing Al-Al with Mg-Si3MgAl3SiO12:Ce3+Yellow powder (non-patent document 4), although the phosphor is Ce relative to LuAG3+The red shift is successfully realized, the emission peak wavelength is about 560nm, however, the white light generated by matching with the blue light chip still has the problem of high color temperature (about 5500K) due to insufficient red shift amplitude. Patent documents 1 to 4 also describe phosphors having a garnet structure, however, these phosphors also have more or less of the above-described problems.
Therefore, it is highly desirable to find a YAG-Ce-doped yttrium aluminum garnet (YAG-Ce) chip which can be strongly excited by a violet-blue light LED chip3+A yellow-orange aluminosilicate fluorescent powder with red shift and higher color rendering index.
Non-patent document 1: ant A. Setlur, Chemistry of Materials, 2006, 18(14): 3314-3322;
non-patent document 2: katelnikovas A, Journal of luminescences, 2009, 129(11): 1356-;
non-patent document 3: pan Z, rsc advances, 2014, 5 (13): 9489-9496:
non-patent document 4: shi Y, Dalton Transactions, 2014,44(4): 1775-1781;
patent document 1: US 2006/0284196 a 1;
patent document 2: CN 104212455A;
patent document 3: CN 104212458A;
patent document 4: WO 2010/043287A 1.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a yellow-orange aluminosilicate fluorescent powder which can be strongly excited by a purple-blue LED chip and can emit light with a tunable peak value between 560nm and 590 nm.
The second purpose of the invention is to provide a preparation method of the garnet-type aluminosilicate fluorescent powder, which is simple and easy to implement.
It is another object of the present invention to provide a light emitting device comprising the garnet-type aluminosilicate phosphor.
In order to achieve the above objects, in one aspect, the present invention provides a garnet-type aluminosilicate phosphor having a chemical formula of (Lu)1-x-yLnxCey)aMgbAlcSidOeWherein a is more than or equal to 1.8 and less than or equal to 2.2, b is more than or equal to 1.8 and less than or equal to 2.1, c is more than or equal to 1.8 and less than or equal to 2.2, d is more than or equal to 1.8 and less than or equal to 2.1, e is more than or equal to 11.8 and less than or equal to 12.2, Ln is one or a combination of more of Sc, Y, Gd and La according to any proportion, x is more than or equal to 0 and less than<y≤0.08。
The garnet type aluminosilicate phosphor of the present invention belongs to a cubic system, Ia-3d space group, and has a general formula A3B2(XO4)3Wherein A, B, X respectively occupies eight-coordination, six-coordination and four-coordination lattice sites, and respectively forms dodecahedral, octahedral and tetrahedral crystal structures with adjacent O atoms. In the fluorescent powder, Lu, Ln, Ce and part of Mg elements occupy eight coordination (A site) sites of crystal lattice, part of Mg and part of Al elements occupy six coordination (B site) sites, and part of Al and Si elements occupy four coordination (X site) sites. By introducing Mg with lower ionic valence and less electronegativity into an eight-coordination (A site) site and a six-coordination (B site) site2+Increase the covalent property between Ce and O and reduce Ce3+The center of gravity of the 5d energy level of (A) and introducing Si having a small ionic radius into the site of the four-coordinate (X-site) lattice4+The crystal field intensity can be enhanced, and the two aspects are beneficial to reducing the energy difference between 5d1-4f and effectively promoting the spectral red shift. Therefore, the fluorescent powder successfully realizes relatively commercial YAG Ce3+The red shift of the wavelength increases the red light component, and the matching with the blue light chip is beneficial to reducing the color temperature.
The main elements contained in the matrix of the phosphor of the present invention are Lu, Mg, Al, Si and O, and the same elements as those contained in the matrix of the phosphor described in non-patent document 4, but the ratio of the same elements contained in the matrix is different from that contained in the matrix, and it is needless to say that the types and contents of the elements occupied by each lattice site are also different. In the phosphor matrix described in non-patent document 4, all elements occupying eight-coordinate (a site) sites are Lu elements, whereas in the present patent, eight-coordinate (a site) sites of the crystal lattice are occupied mainly by Lu and Mg elements; in the phosphor matrix described in non-patent document 4, the Al/Si ratio is 2: 1, and in this patent the ratio is 1: 2. the difference between the phosphor of the present patent and non-patent documents 3, 2 and 3 is that the rare earth element contained in the matrix of the phosphor is mainly Lu, not Y, and the design is intended to: among garnet structures, adjacent dodecahedrons have a feature of being coterminous, so that the closer the ionic radius occupying eight coordination (a site) is, the more favorable it is to form a garnet pure phase, and among trivalent rare earth ions other than Sc, Lu has the smallest radius and the closest radius to Mg ions occupying eight coordination, and too small an average ionic radius occupying eight coordination (a site) makes it difficult to synthesize the garnet structure pure phase under normal pressure conditions, so that it is also impossible to select Sc element having too small an ionic radius as a main rare earth element occupying eight coordination (a site). Based on the consideration of the two aspects on the size of the ionic radius, the Lu element is selected as the main rare earth element occupying eight coordination (A site), which is beneficial to the stable structure, the synthesis of the garnet pure phase structure and the guarantee of better luminescence performance. In addition, Lu has the largest atomic mass among the lanthanide rare earth elements, which is beneficial to enhancing the structural rigidity, so that the thermal stability of the phosphor material can be improved.
Preferably, b: d is 0.95 to 1.05.
The garnet-type aluminosilicate phosphor according to the present invention, wherein b: d is 0.95 to 1.05. The matrix of the fluorescent powder can be seen as being evolved by Mg-Si paired substitution Lu-Al and Mg-Si paired substitution Al-Al on the basis of LuAG, and the number of atoms of Mg and Si is close to each other, so that the valence balance of the whole crystal is maintained, the generation of holes is reduced, and the higher luminous efficiency of the fluorescent powder is ensured.
The garnet-type aluminosilicate fluorescent powder is characterized in that a + b is more than or equal to 3.9 and less than or equal to 4.1. In the fluorescent powder, rare earth ions and partial Mg ions jointly occupy eight coordination (A site) sites of crystal lattices, and the sum of the rare earth ions and the partial Mg ions is too small, so that excessive holes can be generated; the sum of the rare earth ions and the Mg ions is too large, the rare earth ions and the Mg ions are mutually extruded to cause the appearance of a heterogeneous phase, and the two conditions can cause the reduction of the luminous performance of the material, so the sum of the rare earth ions and the Mg ions should be maintained in a proper range, namely, the sum of a and b is more than or equal to 3.9 and less than or equal to 4.1.
The garnet type aluminosilicate fluorescent powder is characterized in that Ln is one or a combination of more of Sc, Y and Gd according to any proportion, preferably Ln is one or two of Y, Gd, and x is more than or equal to 0 and less than or equal to 0.1. Some rare earth ions with the radius larger than that of Lu are properly introduced into the eight coordination site (A site), so that the Ce-O bond length can be compressed, the crystal field strength is enhanced, the spectrum red shift is further realized, and the color rendering index is improved. Compared with other rare earth ions, the radii of Y and Gd are closer to the radius of Lu, the lattice distortion generated by solid solution entering lattice sites is smaller, and the appearance of a hetero phase can be reduced, so that Ln is preferably Y, Gd; however, when Y and Gd are doped in a large amount, a hetero phase occurs and the luminous efficiency is lowered, and therefore, the doping amount is preferably 0. ltoreq. x.ltoreq.0.10.
The inventor finds that the concentration of Ce is limited to a certain extent, on one hand, when the concentration of Ce is too low, the luminous center is too small, and the brightness of the fluorescent powder is low; on the other hand, too much Ce cannot completely enter the lattice site to generate a hetero phase, and concentration quenching occurs between activator Ce entering the lattice to cause a decrease in luminance. Therefore, the Ce concentration is controlled to be in a more appropriate range: y is more than or equal to 0.01 and less than or equal to 0.08; preferably, 0.01. ltoreq. y.ltoreq.0.06.
On the other hand, the invention also provides a preparation method of the garnet-type aluminosilicate fluorescent powder, wherein the fluorescent powder is synthesized by adopting a high-temperature solid-phase method, and the preparation method mainly comprises the following steps:
1) weighing raw materials with the weight corresponding to that of the fluorescent powder according to the stoichiometric ratio, grinding and mixing uniformly;
2) the raw materials are placed in a sintering furnace at 1300-1450 ℃ for high-temperature roasting, and are sintered for 2-10h in a reducing atmosphere;
3) and (3) carrying out post-treatment on the roasted product obtained in the step 2) to obtain the fluorescent powder.
The corresponding raw materials in the step 1) comprise oxides, carbonates and hydroxides;
the high-temperature burning in the step 2) can be carried out for one time or multiple times, the burning temperature is 1300-1450 ℃ every time, and the burning time is 2-10 h;
step 2) the reducing atmosphere is selected from carbon monoxide and nitrogen-hydrogen mixed gas;
and 3) carrying out post-treatment including the processes of manual crushing, ball milling and grinding and particle size classification.
In still another aspect, the present invention also provides a light emitting device comprising the above garnet-type aluminosilicate phosphor. The light-emitting device comprises a radiation source and fluorescent powder, wherein at least one fluorescent powder is selected from the fluorescent powder or the fluorescent powder prepared according to the preparation method.
The light emitting device according to the present invention, wherein the radiation source comprises an ultraviolet, or violet, or blue light emitting source.
Compared with the prior art, the invention has the beneficial effects that: the fluorescent powder is strongly excited by a purple light-blue light LED chip with the wavelength and can emit yellow-orange visible light with adjustable peak value of 560nm to 590nm, and compared with commercial yellow fluorescent powder YAG: Ce3+(540nm) has obvious red shift, and meanwhile, the fluorescent powder has higher quantum efficiency and excellent thermal quenching performance, and can effectively improve the color rendering index and reduce the color temperature when being used for a white light LED. And the fluorescent powder is easy to prepare, does not need harsh conditions and is easy to realize industrial production.
Drawings
FIG. 1 shows example 1 (Lu) of the present invention0.98Ce0.02)2Mg2Al2Si2O12X-ray diffraction spectrum of the fluorescent powder.
FIG. 2 shows example 1 (Lu) of the present invention0.98Ce0.02)2Mg2Al2Si2O12Emission spectrum of phosphor (437nm excitation).
FIG. 3 shows example 1 (Lu) of the present invention0.98Ce0.02)2Mg2Al2Si2O12Excitation spectrum of phosphor (569nm monitoring).
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications can be made by those skilled in the art after reading the contents of the present invention, and those equivalents also fall within the scope of the invention defined by the appended claims.
The following examples will aid understanding of the present invention, but are not intended to limit the scope of the present invention.
Comparative example: y is1.94Ce0.06Mg2Al2Si2O12Preparation of phosphor
Weighing raw material Y according to stoichiometric ratio2O36.1748g、MgO2.2721g、Al2O32.8742g、SiO23.3878g、CeO20.2911g, the raw materials were thoroughly ground in an agate mortar, and then charged into an alumina crucible and charged into a jar with nitrogen2/H2Roasting in reducing atmosphere at 1380 deg.c for 6 hr. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The emission peak wavelength and relative luminous intensity of the phosphor are shown in table 1.
Example 1: (Lu)0.98Ce0.02)2Mg2Al2Si2O12Preparation of phosphor
Weighing raw material Lu according to stoichiometric ratio2O38.3602g、MgO1.7285g、Al2O32.1865g、SiO22.5772g、CeO20.1476g, the raw materials are fully and evenly ground by an agate mortar, then the mixture is put into an alumina crucible and roasted under the CO reducing atmosphere, and the roasting temperature is 1450 ℃ and the temperature is kept for 2 hours. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum wavelength coverage range is 310-520nm, the emission spectrum wavelength coverage range is 480-750nm, and the emission peak wavelength is 569 nm.
Example 2: (Lu)0.81Gd0.15Ce0.04)2Mg2Al1.9Si2.1O12.05Preparation of phosphor
Weighing raw materials according to stoichiometric ratioLu2O36.9643g、Gd2O31.1749g、MgO1.7421g、Al2O32.0936g、SiO22.7274g、CeO20.2976g, the raw materials were thoroughly ground in an agate mortar, and then charged into an alumina crucible and charged into a jar with nitrogen2/H2Roasting in reducing atmosphere at 1350 deg.c for 8 hr. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum wavelength coverage range is 310-520nm, the emission spectrum wavelength coverage range is 480-750nm, and the emission peak wavelength is 585 nm.
Example 3: (Lu)0.91La0.08Ce0.01)1.8Mg2.1Al2.2Si2O12.1Preparation of phosphor
Weighing raw material Lu according to stoichiometric ratio2O37.3020g、La2O30.5246g、MgO1.8968g、Al2O32.5137g、SiO22.6935g、CeO20.0694g, the raw materials are fully and evenly ground by an agate mortar, then are put into an alumina crucible, and are roasted twice in a CO reducing atmosphere, and the temperature is maintained at 1400 ℃ for 2 hours for the first time; naturally cooling, crushing, grinding, roasting for the second time, and keeping the temperature at 1350 ℃ for 7 hours. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum wavelength coverage range is 310-520nm, the emission spectrum wavelength coverage range is 480-750nm, and the emission main peak is 573 nm.
Example 4: (Lu)0.92Sc0.05Ce0.03)2.1Mg1.9Al2.1Si1.9O12Preparation of phosphor
Weighing raw material Lu according to stoichiometric ratio2O38.2326g、Sc2O30.1551g、MgO1.6404g、Al2O32.2936g、SiO22.4660g、CeO20.2322g, the raw materials were thoroughly ground in an agate mortar, and then charged into an alumina crucible and charged into a jar with nitrogen2/H2Roasting in reducing atmosphereThe firing temperature was 1300 ℃ and the temperature was maintained for 10 hours. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum wavelength coverage range is 310-520nm, the emission spectrum wavelength coverage range is 480-750nm, and the emission main peak is 568 nm.
Example 5: (Lu)0.84La0.05Sc0.05Ce0.06)2Mg1.8Al2Si2O11.8Preparation of phosphor
Weighing raw material Lu according to stoichiometric ratio2O37.4517g、La2O30.3625g、Sc2O30.1538g、MgO1.6177g、Al2O32.2737g、SiO22.6801g、CeO20.4605g, fully and uniformly grinding the raw materials by using an agate mortar, then putting the raw materials into an alumina crucible, roasting the raw materials for three times in a CO reducing atmosphere, and keeping the temperature of the first roasting at 1400 ℃ for 2 hours; naturally cooling, crushing, grinding, roasting for the second time, and keeping the temperature at 1350 ℃ for 6 hours; naturally cooling, crushing, grinding, roasting for the second time, and keeping the temperature at 1300 ℃ for 5 hours. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum wavelength coverage range is 310-520nm, the emission spectrum wavelength range is 480-750nm, and the main emission peak is 578 nm.
Example 6: (Lu)0.86Y0.1Ce0.04)2.1Mg2Al1.8Si2O11.85Preparation of phosphor
Weighing raw material Lu according to stoichiometric ratio2O37.8098g、Y2O30.5155g、MgO1.7524g、Al2O31.9951g、SiO22.6129g、CeO20.3143g, the raw materials were thoroughly ground in an agate mortar, and then charged into an alumina crucible and charged into a jar with nitrogen2/H2Roasting in reducing atmosphere at 1380 deg.c for 5 hr. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum has a wavelength coverage range of310-520nm, the coverage range of the emission spectrum wavelength is 480-750nm, and the main emission peak is 579 nm.
Example 7: (Lu)0.89Gd0.075Ce0.035)2Mg1.8Al2Si2.1O12Preparation of phosphor
Weighing raw material Lu according to stoichiometric ratio2O37.6527g、Gd2O30.5875g、MgO1.5680g、Al2O32.2039g、SiO22.7276g、CeO20.2604g, the raw materials are fully ground by an agate mortar, then the mixture is put into an alumina crucible and roasted under the atmosphere of CO reduction, and the roasting temperature is 1370 ℃ and the temperature is kept for 5 hours. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum wavelength coverage range is 310-520nm, the emission spectrum wavelength coverage range is 480-750nm, and the emission main peak is 581 nm.
Example 8: (Lu)0.77Y0.1Gd0.05Ce0.08)2.2Mg2.1Al2Si1.8O12Preparation of phosphor
Weighing raw material Lu according to stoichiometric ratio2O37.1511g、Y2O30.5272g、Gd2O30.4230g、MgO1.7962g、Al2O32.1640g、SiO22.2956g、CeO20.6429g, the raw materials are fully ground by an agate mortar, then the mixture is put into an alumina crucible and roasted under the reducing atmosphere of N2/H2, and the roasting temperature is 1380 ℃ and the temperature is kept for 5 hours. After natural cooling, the fluorescent powder with corresponding composition is obtained after the post-treatment of crushing, ball milling, sieving, washing, drying and the like. The excitation spectrum wavelength coverage range is 310-520nm, the emission spectrum wavelength coverage range is 480-750nm, and the emission main peak is 590 nm.
Example 9: the phosphor obtained in example 1 was dispersed in a resin, and applied to an InGaN blue LED chip of 455nm after being mixed with a paste, cured, and soldered with a circuit, and sealed with a resin, to obtain a white light emitting device having color coordinates (0.3465,0.3196), a color rendering index of 83.7, and a correlated color temperature of 4759K.
Example 10: the phosphor obtained in example 7 was dispersed in a resin, and after slurry mixing, the phosphor was coated on an InGaN blue LED chip of 455nm, cured, and soldered with a circuit, and sealed with a resin, to obtain a white light emitting device having color coordinates (0.3627, 0.3317), color rendering index 85.9, and correlated color temperature 4493K.
TABLE 1 chemical compositions, emission main peak position under 450nm excitation and relative luminescence intensity (450 nm excitation (Lu) is selected) for examples 1-8 and comparative examples0.98Ce0.02)2Mg2Al2Si2O12Luminous intensity of (2) is 100%)
The phosphors of examples 1-8 of the present invention are strongly excited by the violet-blue LED chip and emit peak wavelengths of 560nm to 590nm, although having a certain blue shift with respect to the comparative example, but are YAG: Ce, which is a commercial yellow phosphor3+(540nm) has obvious red shift, and can effectively improve the color rendering index and reduce the color temperature when being used for a white light LED. Significantly, compared with the comparative example, the example of the invention has higher quantum efficiency and more excellent thermal quenching performance, and therefore, has better application value. And the fluorescent powder is easy to prepare, does not need harsh conditions and is easy to realize industrial production.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (12)
1. An aluminosilicate garnet-type phosphor characterized in that: the chemical formula is (Lu)1-x-yLnxCey)aMgbAlcSidOeWherein a is more than or equal to 1.8 and less than or equal to 2.2,b is more than or equal to 1.8 and less than or equal to 2.1, c is more than or equal to 1.8 and less than or equal to 2.2, d is more than or equal to 1.8 and less than or equal to 2.1, e is more than or equal to 11.8 and less than or equal to 12.2, Ln is one or a combination of more of Sc, Y, Gd and La according to any proportion, 0<x≤0.15，0<y≤0.08。
2. The phosphor of claim 1, wherein b: d is 0.95 to 1.05.
3. The phosphor of claim 1, wherein 3.9 ≦ a + b ≦ 4.1.
4. The phosphor of any of claims 1-3, wherein Ln is selected from one or two of Y, Gd, 0< x ≦ 0.1.
5. The phosphor of any of claims 1-3, wherein 0.01 ≦ y ≦ 0.06.
6. A method of making the phosphor of any of claims 1-5, wherein: the fluorescent powder is synthesized by adopting a high-temperature solid-phase method, and mainly comprises the following steps:
1) weighing raw materials with the weight corresponding to that of the fluorescent powder according to the stoichiometric ratio, grinding and mixing uniformly;
2) the raw materials are placed in a sintering furnace at 1300-1450 ℃ for high-temperature roasting, and are sintered for 2-10h in a reducing atmosphere;
3) and (3) carrying out post-treatment on the roasted product obtained in the step 2) to obtain the fluorescent powder.
7. The method of claim 6, wherein the raw material of step 1) comprises corresponding oxide, carbonate, hydroxide.
8. The method for preparing the phosphor according to claim 6, wherein the high temperature calcination in the step 2) is performed one or more times, the calcination temperature is 1300 ℃ to 1450 ℃, and the calcination time is 2 to 10 hours.
9. The method according to claim 6, wherein the reducing atmosphere of step 2) is selected from a mixture of carbon monoxide and hydrogen nitrogen.
10. A light emitting device comprising a radiation source and a phosphor, characterized in that: at least one phosphor is selected from the phosphors according to any one of claims 1 to 5 or the phosphors prepared by the preparation method according to any one of claims 6 to 9.
11. The light emitting device of claim 10, the radiation source comprising a violet, or blue, radiation source.
12. The light emitting device of claim 10, the radiation source being an ultraviolet emission source.
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