CN106497557A - A kind of short wavelength silicate green fluorescent powder of efficient stable and preparation method and application - Google Patents
A kind of short wavelength silicate green fluorescent powder of efficient stable and preparation method and application Download PDFInfo
- Publication number
- CN106497557A CN106497557A CN201610944763.0A CN201610944763A CN106497557A CN 106497557 A CN106497557 A CN 106497557A CN 201610944763 A CN201610944763 A CN 201610944763A CN 106497557 A CN106497557 A CN 106497557A
- Authority
- CN
- China
- Prior art keywords
- short wavelength
- fluorescent powder
- green fluorescent
- efficient stable
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 26
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 108010043121 Green Fluorescent Proteins Proteins 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 12
- 239000011265 semifinished product Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- 229910016644 EuCl3 Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims 5
- 238000005286 illumination Methods 0.000 claims 1
- 238000010791 quenching Methods 0.000 abstract description 12
- 230000000171 quenching effect Effects 0.000 abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 229910052909 inorganic silicate Inorganic materials 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000004907 flux Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910001632 barium fluoride Inorganic materials 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000012459 muffins Nutrition 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910001637 strontium fluoride Inorganic materials 0.000 description 2
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000000751 Chenopodium murale Nutrition 0.000 description 1
- 244000191502 Chenopodium murale Species 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000605159 Nitrobacter Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical group [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- -1 has YAG types Chemical compound 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- 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
-
- 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
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides short wavelength's silicate green fluorescent powder of a kind of efficient stable and preparation method and application, the chemical general formula of the fluorescent material is Ba2‑x‑z‑q‑2nMxNanGanSiyO4:zEu,qMn；In formula, M is at least one in Zn, Mg, Ca, and 0≤x≤0.3,0.001≤n≤0.1,0.8≤y≤1.2,0.005≤z≤0.15,0.01≤q≤0.04.The present invention is using multiplexed combinations such as Na, Ga, alkaline-earth metal, Mn elements, regulation is optimized to the crystalline field of fluorescent material, and using special composite assistants high temperature sintering, the position of transmitting main peak not only can be adjusted, the short wavelength range of 500 ~ 525nm is obtained, and pure single-phase is obtained, substantially increase luminous intensity and the crystallization degree of fluorescent material, no matter high temperature thermal quenching performance, or moisture-resistant hot property is well positioned to meet the requirement of white light LEDs, meanwhile, also add product yield.
Description
Technical field
The present invention relates to a kind of green emitting phosphor and preparation method thereof, and in particular to a kind of short wavelength's silicic acid of efficient stable
Salt green emitting phosphor and preparation method and application.
Background technology
At present, the white light LEDs of main flow are to excite YAG using InGaN blue chips:Ce3+Fluorescent material produces complementary with blue light
Gold-tinted so that mix to realize.But, due to YAG:Ce3+In fluorescent material, red-light spectrum energy accounts for the 8 of total spectral energy
～15%, far below the ratio of green-yellow light, the product colour rendering index for manufacturing in this way low (typically 70 or so), and
With the optimum visual of human eye, colour temperature higher (substantially in more than 5500K), requires that (3000～5000K) has certain deviation, therefore
It is not used to domestic lighting.For this purpose, researcher passes through to YAG:Ce3+Middle add rouge and powder with reach lifted colour rendering index mesh
, but, be the regulation that impossible realize full spectrum only by the combination of existing bloom+rouge and powder, based on colorimetry in terms of grind
Study carefully analysis, this is relatively weak caused mainly due to the intensity in green glow S-band.
Existing green emitting phosphor mainly has YAG types, β-Sialon types and silicate-type, and the half-peak breadth of YAG systems is wider,
Color saturation is relatively low, is extremely difficult to the requirement of NTSC standard value, and the synthesis condition of β-Sialon system green emitting phosphors is suitable
Harshness, and preparation cost is high, the half-peak width of silicate systems, but stability and high temperature quenching poor performance.Therefore, more
New matrix is stable, synthesis condition is simple, cost is relatively low, yield is higher and the good, good luminous performance of half-peak width, crystal formation etc. is comprehensive
The white light LEDs for closing excellent performance are the base material of active demand in industry with short wavelength's green emitting phosphor.
A kind of formula is disclosed in CN201110307939.9 for SrxBa(2-x-y-z)EuyMzSipO(2+2p)Silicate green
Fluorescent material, its pass through to change the different doped chemical of Coprecipitation and interpolation through screening, dispersant and organic solvent, obtain
A kind of crystal formation crystalline substance looks are good, be close to spherical, even particle size distribution and controllable green emitting phosphor, but the hot-quenching of the fluorescent material is gone out
Performance and heat resistance poor-performing.CN201110209942.7 takes three steps to synthesize formula for (A, B)2-xSiO4:The silicon of xEu
Hydrochlorate green emitting phosphor, wherein 0 ＜ x ＜ 2.0, element A are Ca or Sr, and B element is Ba, and flux used by which is fluoride, sends out
Penetrate peak wavelength adjustable in 518-545nm.In CN201010214878.7, molecular formula is Ba(2-x-y-p)SrxMpSiqO(2+2q):
Euy, wherein, M is at least one in Sc, Y, La, Cr or Er, effectively lifts the emissive porwer of fluorescent material, and flux is NH4F,
The minimal wave length of products obtained therefrom is 520nm.Fluorescent material peak wavelength obtained by above-mentioned prior art is partially long, in preparation process
Flux used is the stronger fluoride of corrosivity, and the luminous intensity of product, high temperature thermal quenching performance and moisture resistance
Can be not good enough.
Content of the invention
It is an object of the invention to provide short wavelength's silicate green fluorescent powder of a kind of efficient stable and preparation method thereof,
To solve the problems, such as existing green emitting phosphor peak wavelength long, luminous efficiency low and high temperature quenching performance and heat resistance poor performance partially.
The object of the present invention is achieved like this：
A kind of short wavelength's silicate green fluorescent powder of efficient stable, the chemical general formula of the fluorescent material is Ba2-x-z-q- 2nMxNanGanSiyO4:zEu,qMn；In formula, M is at least one in Zn, Mg, Ca, and 0≤x≤0.3,0.001≤n≤0.1,
0.8≤y≤1.2,0.005≤z≤0.15,0.01≤q≤0.04.Preferably, 0.01≤x≤0.2,0.01≤n≤0.05,
0.95≤y≤1.05,0.01≤z≤0.1,0.01≤q≤0.03.
The fluorescent material of the present invention has the short wavelength range of 500～525nm, while it is sudden to have high, the high warm of luminous efficiency concurrently
The features such as performance of going out is good, moisture-resistant good in thermal property, chemical stability are good, after encapsulation, double 85 light efficiency reduced rates of LED are less than 2%, energy
Enough requirements for meeting white light LEDs well.
The present invention a kind of preparation method of short wavelength's silicate green fluorescent powder of above-mentioned efficient stable is also provided, including with
Lower step：
A, raw material are weighed：According to chemical general formula Ba2-x-z-q-2nMxNanGanSiyO4:The mol ratio of each element in zEu, qMn
Weigh metal carbonate or metal oxide starting material containing Ba, M, Na, Ga, Si, Eu, Mn；
B, auxiliary agent are weighed：Weigh ZnCl2/EuCl3·6H2O composite assistants, the quality of the composite assistants is institute in step a
Have the 1～5% of raw material gross mass；
C, mixing：The raw material weighed in step a is mixed with the composite assistants dry ball milling weighed in step b
Even, it is then placed in aluminum oxide Noah's ark；
D, sintering：Above-mentioned aluminum oxide Noah's ark is placed in vacuum tube furnace, is evacuated to less than 10Pa, is then filled with 0 ＜
It is normal pressure that the speed of gas speed≤10MPa carries out also Primordial Qi tonifying Qi to furnace pressure Ρ, this step in triplicate, then in reduction
1250 DEG C are warming up under atmosphere, 1～4h is incubated, and then cooling is annealed to 1000 DEG C, then naturally cools to room temperature, grinds, and crosses 200
Mesh sieve, obtains final product fluorescent material semi-finished product；
E, post processing：First with ammonia aqueous solution washing by soaking fluorescent material semi-finished product, it is 6～7 to be washed with water to cleaning solution pH
Afterwards, vacuum filtration, then heating, drying, obtains final product short wavelength's silicate green fluorescent powder of efficient stable.
In step c of the inventive method, Ball-milling Time is 5～10h.
In step d of the inventive method, reducing atmosphere is 100% pure hydrogen atmosphere.
In step d of the inventive method, heating rate is 10 DEG C/min, and rate of temperature fall is 3 DEG C/min.
Post processing in step e of the inventive method is referred to the fluorescent powder after ground sieving in pH=9
Ammonia aqueous solution in the rotating speed of 400r/min stirring 3h, wherein solid-to-liquid ratio is 1g: 12mL, and stirring is washed to washing after terminating
Liquid pH is 6-7, finally carries out vacuum filtration, by suction filtration after muffin dries 4h at 70 DEG C, obtain final product after crossing 200 mesh sieves efficiently surely
Fixed short wavelength's silicate green fluorescent powder finished product.
The present invention is optimized to the crystalline field of fluorescent material using multiplexed combinations such as Na, Ga, alkaline-earth metal, Si, Mn elements
Adjust, and using special composite assistants high temperature sintering, the position of transmitting main peak not only can be adjusted, obtain 500～525nm's
Short wavelength range, and pure single-phase is obtained, luminous intensity and the crystallization degree of fluorescent material is substantially increased, no matter high
Warm quenching performance, or moisture-resistant hot property is well positioned to meet the requirement of white light LEDs, meanwhile, also add product yield.
Short wavelength's green fluorescence pruinescence of the invention is ultraviolet, purple light or blue light are effectively excited, and is applied to illuminate or show system
In system.
Description of the drawings
Fig. 1 is the launching light spectrogram of fluorescent material prepared by embodiment 1,14 and 27.
Fig. 2 is the thermal quenching curve of the embodiment 1 of peak value 510nm and the luminous intensity of fluorescent material prepared by Reference Example 1.
Fig. 3 is the thermal quenching curve of the embodiment 27 of peak value 520nm and the luminous intensity of fluorescent material prepared by Reference Example 2.
Fig. 4 is the thermal quenching curve of the embodiment 36 of peak value 525nm and the luminous intensity of fluorescent material prepared by Reference Example 3.
Fig. 5 is the SEM figures of fluorescent material prepared by Reference Example 3.
Fig. 6 is the SEM figures of fluorescent material prepared by embodiment 36.
Specific embodiment
The chemical general formula of short wavelength's silicate green fluorescent powder of the efficient stable that the present invention is provided is
Ba2-x-z-q-2nMxNanGanSiyO4:zEu,qMn；In formula, M is at least one in Zn, Mg, Ca, and 0≤x≤
0.3,0.001≤n≤0.1,0.8≤y≤1.2,0.005≤z≤0.15,0.01≤q≤0.04.Preferably, 0.01≤x≤
0.2,0.01≤n≤0.05,0.95≤y≤1.05,0.01≤z≤0.1,0.01≤q≤0.03.
The preparation method of above-mentioned fluorescent material is comprised the following steps：
A, raw material are weighed：According to chemical general formula Ba2-x-z-q-2nMxNanGanSiyO4:The mol ratio of each element in zEu, qMn
Weigh metal carbonate or metal oxide starting material containing Ba, M, Na, Ga, Si, Eu, Mn；
B, auxiliary agent are weighed：Weigh ZnCl2/EuCl3·6H2O composite assistants, the quality of the composite assistants is institute in step a
Have the 1～5% of raw material gross mass；
C, mixing：The raw material weighed in step a is mixed with the composite assistants dry ball milling weighed in step b
Even, it is then placed in aluminum oxide Noah's ark；
D, sintering：Above-mentioned aluminum oxide Noah's ark is placed in vacuum tube furnace, is evacuated to less than 10Pa, is then filled with 0 ＜
It is normal pressure that the speed of gas speed≤10MPa carries out also Primordial Qi tonifying Qi to furnace pressure Ρ, this step in triplicate, then in reduction
1250 DEG C are warming up under atmosphere, 1～4h is incubated, and then cooling is annealed to 1000 DEG C, then naturally cools to room temperature, grinds, and crosses 200
Mesh sieve, obtains final product fluorescent material semi-finished product；
E, post processing：By the fluorescent powder after ground sieving in the ammonia aqueous solution of pH=9 with 400r/min turn
Speed stirring 3h, wherein solid-to-liquid ratio are 1g: 12mL, and stirring is washed to cleaning solution pH for 6-7 after terminating, finally carry out vacuum filtration,
Muffin after by suction filtration dries 4h at 70 DEG C, obtains final product short wavelength's silicate green fluorescent powder of efficient stable after crossing 200 mesh sieves
Finished product.
The instrument that testing graininess in the present invention is adopted is laser particle analyzer LS-C (I), the instrument that relative luminance test is adopted
Device is high accuracy fast spectrum radiometer.
K=(D90-D10)/D50For weighing grain graininess uniformity coefficient, K values are less, represent that grain graininess is more uniform.
Quality (fluorescent material finished product) after yield=post processing before the quality (fluorescent material crude product) of resulting materials/post processing.
The present invention is expanded on further with reference to specific embodiment, in following embodiment, do not described in detail is various
Process and method are conventional methods as known in the art, and agents useful for same is that commercially available analysis is pure or chemical pure.
Embodiment 1：Ba1.86Zn0.076Na0.02Ga0.02Si0.98O4:The preparation of 0.04Eu, 0.024Mn fluorescent material.
According to chemical general formula Ba1.86Zn0.076Na0.02Ga0.02Si0.98O4:The mol ratio of each element in 0.04Eu, 0.024Mn
BaCO is weighed respectively3、MgCO3、Na2CO3、Ga2O3、SiO2、Eu2O3、MnCO3Raw material, material purity is 99.99%；Then
Weigh ZnCl2/EuCl3·6H2O composite assistants (wherein ZnCl2With EuCl3·6H2The mass ratio of O is 1: 0.1), composite assistants
Addition for raw material gross mass 2%；By composite assistants and raw material dry ball milling 8h, the material being well mixed is put into oxygen then
Change in aluminium Noah's ark；The aluminum oxide Noah's ark that will be equipped with material is placed in vacuum tube furnace, is evacuated to less than 10Pa, then with 0 ＜
It is normal pressure that the speed of inflation rate≤10MPa carries out also Primordial Qi tonifying Qi to furnace pressure Ρ, this step in triplicate, Ran Hou
With the ramp of 10 DEG C/min to 1250 DEG C under 100% pure hydrogen reducing atmosphere, 2.5h, then the speed with 3 DEG C/min is incubated
Rate naturally cools to room temperature after being cooled to 1000 DEG C, then ground, obtains fluorescent material semi-finished product after crossing 200 mesh sieves；By fluorescent material
With the rotating speed stirring 3h of 400r/min in the ammonia aqueous solution of pH=9, wherein solid-to-liquid ratio is 1g: 12mL to semi-finished product, stirring knot
Cleaning solution pH is washed to after beam for 6-7, vacuum filtration is finally carried out, by suction filtration after muffin dry 4h at 70 DEG C, after 200
Mesh sieve, that is, obtain Ba1.86Zn0.076Na0.02Ga0.02Si0.98O4:0.04Eu, 0.024Mn silicate green fluorescent powder.The fluorescent material
Transmitting main peak be located at 510nm near, as shown in figure 1, relative intensity be 135%.
Embodiment 2～6：Ba1.86Zn0.076Na0.02Ga0.02Si0.98O4:The preparation of 0.04Eu, 0.024Mn fluorescent material.
Change the addition of composite assistants, other conditions with embodiment 1, are tested to obtained fluorescent material, institute
1 must be the results are shown in Table, without composite assistants, other conditions are same as Example 1 for the comparative example 1 in table.
Table 1
Embodiment 7～15, comparative example 2
Change the content of Na and Ga, other conditions with embodiment 1, are tested to obtained fluorescent material, gained is tied
Fruit is shown in Table 2.
Table 2
Embodiment 13～17
M is Mg, changes the content of Mg, and other conditions with embodiment 1, are tested to obtained fluorescent material, gained
The results are shown in Table 3.
Table 3
Embodiment 18～23
M is Zn, changes the content of Zn, and other conditions with embodiment 1, are tested to obtained fluorescent material, gained
The results are shown in Table 4.
Table 4
Embodiment 24～29
M is Ca, changes the content of Ca, and other conditions with embodiment 1, are tested to obtained fluorescent material, gained
The results are shown in Table 5.
Table 5
Embodiment 30～37
Change the content of Eu and the species of M, other process conditions with embodiment 1, are surveyed to obtained fluorescent material
Examination, acquired results are shown in Table 6, and the scanning electron microscope (SEM) photograph of embodiment 36 is shown in Fig. 6.
Table 6
Embodiment 38～42
Change the content of Mn, other conditions with embodiment 1, are tested to obtained fluorescent material, and acquired results are shown in
Table 7.
Table 7
Reference Example 1：Sr is prepared according to document CN201110307939.90.8Ba1.16SiO4:Eu0.04Fluorescent material.
1) strontium oxide strontia 23.621g, barium monoxide 45.782g and europium oxide 1.408g is weighed, is dissolved in nitric acid, form rare earth gold
Genus nitrobacter solution A1；
2) heated solution A1To 40 DEG C, solution A is stirred continuously1, sal volatile is slowly added into solution A1In, add few
Dispersant made by amount ethanol, at the uniform velocity stirs to reaction completely, obtains metal carbonate precipitate thing B1, this process is by adding ammoniacal liquor guarantor
The pH value for holding precipitation body is 7～8；
3) by metal carbonate precipitate thing B1Filter, 120 DEG C of drying are then charged into being put into Muffle furnace in alumina crucible
In, 600 DEG C of insulation 2h obtain pure carbonate sediment C1；
4) composition formula Sr is pressed0.8Ba1.16SiO4:Eu0.04 quantitatively weighs pure carbonate sediment C1And silica
12.017g, add carbonate sediment C1And the barium fluoride of the 0.5% of silica gross mass makees auxiliary agent, by above-mentioned mixing
Raw material is put in ball grinder, is added agate ball and 50ml absolute ethyl alcohols, is sufficiently mixed1；
5) by suspension D1Suction filtration, 120 DEG C of drying, crushing sieve, precursor material E being uniformly mixed1；
6) by presoma E1It is placed in reduction furnace, adjusts N2For 195ml/min, H2For 5ml/min, 1350 DEG C of insulation 4h, obtain
Arrive powder F1, then to dismiss naturally in deionized water, last deionized water is washed till neutrality, dries, that is, obtains finished product.
The peak wavelength of products obtained therefrom is 510nm, and particle diameter is 15 μm, and K values are 1.3, and relative luminance is 100.
Reference Example 2：Sr is prepared according to document CN201110307939.90.97Ba0.97SiO4:Eu0.06Fluorescent material.
With Reference Example 1, the peak wavelength of products obtained therefrom is 520nm to preparation method, and particle diameter is 20 μm, and K values are 1.4, relative
Brightness is 105.6.
Reference Example 3：Sr is prepared according to embodiment 2 in document CN201110209942.70.98BaSiO4:0.02Eu fluorescent material.
1) precursor Sr2SiO4Preparation：According to Sr2SiO4Stoichiometric proportion, weigh SrCO3147.61g、
SiO230.04g mixes, and is fully ground and obtains first time mixture；The flux of its quality 3% is added in first time mixture
SrF2, blended, be fully ground after be put in alumina crucible, crucible is placed in tube furnace, in protective gas N2In with 1250
Cooling after DEG C temperature sintering 3h obtains precursor Sr2SiO4, gas flow is 20ml/min；
2) precursor Ba2SiO4Preparation：According to Ba2SiO4Stoichiometric proportion, weigh BaCO3100g、SiO215.23g
Mixing, is fully ground and obtains second mixture；The flux BaF of its quality 2% is added in second mixture2, through mixed
Close, be fully ground after be put in alumina crucible, crucible is placed in tube furnace, in protective gas NH3In with 1000 DEG C of temperature
Cooling after sintering 3h obtains precursor Ba2SiO4, gas flow is 20ml/min；
3) adulterate in the matrix structure that two kinds of precursors are provided Eu elements, synthesizes green emitting phosphor Sr0.98BaSiO4:
0.02Eu：According to stoichiometric proportion, by gained Sr2SiO4After grinding is sieved, 20g, Ba is weighed2SiO4After grinding is sieved, weigh
28g, then weigh Eu2O30.537g and SiO20.092g, finally adds the SrF of 5% (in terms of mixed third time mixture)2
With BaF2Mixed aid, SrF2∶BaF2=1: 2, it is put in molybdenum crucible after above-mentioned each composition grinding, molybdenum crucible is moved into high temperature
In tube furnace, in N2∶H2Lower 1400 DEG C of=3: 1 atmosphere is sintered 4.5 hours, and its gas flow is 35ml/min, is cooled to room afterwards
Temperature is taken out after drying through ethanol washing after grinding is sieved and obtains final product silicate green fluorescent powder Sr0.98BaSiO4:0.02Eu.The green
Emission wavelength after fluorescent material is excited is 525nm；Its scanning electron microscope (SEM) photograph is as shown in Figure 5.
Comparative example 4：By the fluorescent material semi-finished product obtained by preparation technology same as Example 1 (at ammoniacal liquor
Semi-finished product after the sieving of reason), obtained fluorescent material semi-finished product are carried out with high temperature thermal quenching performance and double 85 experiment tests.
High temperature thermal quenching performance test：Respectively to the product obtained by embodiment 1,14,27,33 and 36, Reference Example 1,2,3
And product obtained in comparative example 1,2,3,4 carries out thermal quenching detection, test mode is：With the external temperature-controlling systems of F7000, first rise
Then temperature tests the emission spectrum of each temperature spot in temperature-fall period to 500K, and detection temperature is 300K～500K, as a result sees
Table 8, Fig. 2, Fig. 3 and Fig. 4.
Table 8
It can thus be seen that the high temperature stability performance of the product prepared by the present invention is substantially better than Reference Example and comparative example institute
Obtain product.
Double 85 experiment tests：Weigh respectively product obtained by embodiment 1,14,27,33 and 36, Reference Example 1,2,3 and
The each 10g of product obtained in comparative example 1,3,4, temperature be 85 DEG C, humidity be to carry out double 85 experiments in the environment of 85%, be interrupted into
Every 200h, row 1000h, with relative luminance and x chromaticity coordinates as Testing index, detects that once test result is shown in Table 9, table 10.
Table 9
Table 10
Data in by upper table can be seen that products obtained therefrom of the present invention and show more preferable moisture-resistant hot property, its stability
It is substantially better than 1,3,4 products obtained therefrom of Reference Example 1,2,3 and comparative example.
Claims (8)
1. short wavelength's silicate green fluorescent powder of a kind of efficient stable, it is characterised in that the chemical general formula of the fluorescent material is
Ba2-x-z-q-2nMxNanGanSiyO4:zEu,qMn；In formula, M is at least one in Zn, Mg, Ca, and 0≤x≤0.3,0.001≤
N≤0.1,0.8≤y≤1.2,0.005≤z≤0.15,0.01≤q≤0.04.
2. the preparation method of short wavelength's silicate green fluorescent powder of a kind of efficient stable, it is characterised in that comprise the following steps：
A, raw material are weighed：According to chemical general formula Ba2-x-z-q-2nMxNanGanSiyO4:In zEu, qMn, the mol ratio of each element is weighed
Metal carbonate or metal oxide starting material containing Ba, M, Na, Ga, Si, Eu, Mn；
B, auxiliary agent are weighed：Weigh ZnCl2/EuCl3·6H2O composite assistants, the quality of the composite assistants is all originals in step a
The 1 ~ 5% of material gross mass；
C, mixing：The raw material weighed in step a is well mixed with the composite assistants dry ball milling weighed in step b, so
After be put in aluminum oxide Noah's ark；
D, sintering：Above-mentioned aluminum oxide Noah's ark is placed in vacuum tube furnace, 1250 DEG C are warming up under reducing atmosphere, insulation 1 ~
4h, then cooling are annealed to 1000 DEG C, then naturally cool to room temperature, grind, and cross 200 mesh sieves, obtain final product fluorescent material semi-finished product；
E, post processing：First with ammonia aqueous solution washing by soaking fluorescent material semi-finished product, it is washed with water to cleaning solutionpAfter H is 6 ~ 7, very
Empty suction filtration, then heating, drying, obtains final product short wavelength's silicate green fluorescent powder of efficient stable.
3. the preparation method of short wavelength's silicate green fluorescent powder of efficient stable according to claim 2, its feature exist
In, in step c, Ball-milling Time is 5 ~ 10h.
4. the preparation method of short wavelength's silicate green fluorescent powder of efficient stable according to claim 2, its feature exist
In, in step d, reducing atmosphere is 100% pure hydrogen atmosphere.
5. the preparation method of short wavelength's silicate green fluorescent powder of efficient stable according to claim 2, its feature exist
In, in step d, heating rate is 10 DEG C/min, and rate of temperature fall is 3 DEG C/min.
6. the preparation method of short wavelength's silicate green fluorescent powder of efficient stable according to claim 2, its feature exist
In, in step e, ammonia aqueous solution washing by soaking be by fluorescent material semi-finished product inp3h is stirred in the ammonia aqueous solution of H=9,
Rotating speed is 400r/min, and solid-to-liquid ratio is 1g: 12mL.
7. the preparation method of short wavelength's silicate green fluorescent powder of efficient stable according to claim 2, its feature exist
In, in step e, drying temperature is 70 DEG C, and drying time is 4h.
8. a kind of short wavelength's silicate green fluorescent powder of the efficient stable described in claim 1 is had by ultraviolet, purple light or blue light
Imitate the application in illumination or display system after exciting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610944763.0A CN106497557B (en) | 2016-11-02 | 2016-11-02 | A kind of short wavelength's silicate green fluorescent powder of efficient stable and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610944763.0A CN106497557B (en) | 2016-11-02 | 2016-11-02 | A kind of short wavelength's silicate green fluorescent powder of efficient stable and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106497557A true CN106497557A (en) | 2017-03-15 |
| CN106497557B CN106497557B (en) | 2019-02-05 |
Family
ID=58322946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610944763.0A Active CN106497557B (en) | 2016-11-02 | 2016-11-02 | A kind of short wavelength's silicate green fluorescent powder of efficient stable and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106497557B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108183099A (en) * | 2017-12-21 | 2018-06-19 | 厦门市三安光电科技有限公司 | A kind of White-light LED package structure and white light source system |
| CN116217260A (en) * | 2022-12-06 | 2023-06-06 | 四川省交通建设集团有限责任公司 | Self-luminous ceramsite, preparation method and self-luminous ultrathin wearing layer containing self-luminous ceramsite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101053478B1 (en) * | 2008-12-01 | 2011-08-04 | 루시미아 주식회사 | Full color phosphor and its manufacturing method |
| KR20130090127A (en) * | 2012-02-03 | 2013-08-13 | 한국과학기술원 | New composition of aluminum silicate phosphor and preparing method |
| CN105295916A (en) * | 2015-12-03 | 2016-02-03 | 河北利福光电技术有限公司 | Green silicate phosphor as well as preparation method and application of green silicate phosphor |
-
2016
- 2016-11-02 CN CN201610944763.0A patent/CN106497557B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101053478B1 (en) * | 2008-12-01 | 2011-08-04 | 루시미아 주식회사 | Full color phosphor and its manufacturing method |
| KR20130090127A (en) * | 2012-02-03 | 2013-08-13 | 한국과학기술원 | New composition of aluminum silicate phosphor and preparing method |
| CN105295916A (en) * | 2015-12-03 | 2016-02-03 | 河北利福光电技术有限公司 | Green silicate phosphor as well as preparation method and application of green silicate phosphor |
Non-Patent Citations (1)
| Title |
|---|
| HUANG SHAN 等: "Luminescence properties of a single-host phosphor Ba1.8–wSrwLi0.4SiO4: Ce3+,Eu2+,Mn2+ for WLED", 《JOURNAL OF RARE EARTHS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108183099A (en) * | 2017-12-21 | 2018-06-19 | 厦门市三安光电科技有限公司 | A kind of White-light LED package structure and white light source system |
| CN116217260A (en) * | 2022-12-06 | 2023-06-06 | 四川省交通建设集团有限责任公司 | Self-luminous ceramsite, preparation method and self-luminous ultrathin wearing layer containing self-luminous ceramsite |
| CN116217260B (en) * | 2022-12-06 | 2024-04-19 | 四川省交通建设集团有限责任公司 | Self-luminous ceramsite, preparation method and self-luminous ultrathin wearing layer containing self-luminous ceramsite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106497557B (en) | 2019-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Double perovskite Ba2LaNbO6: Mn4+, Yb3+ phosphors: potential application to plant-cultivation LEDs | |
| Yongqing et al. | Properties of red-emitting phosphors Sr2MgSi2O7: Eu3+ prepared by gel-combustion method assisted by microwave | |
| Yang et al. | Tunable blue-green color emission and energy transfer of Sr3NaSc (PO4) 3F: Eu2+, Tb3+ phosphors with near-UV broad band excited for white LEDs | |
| CN101760194B (en) | Red fluorescent powder used by white light LED and preparation method thereof | |
| CN101307228B (en) | Chlorine-aluminosilicate fluorescent powder and method for preparing same | |
| CN106497557B (en) | A kind of short wavelength's silicate green fluorescent powder of efficient stable and the preparation method and application thereof | |
| JP2003027056A (en) | Pink color developing device | |
| CN110028964A (en) | A kind of white light LEDs apatite structure blue light fluorescent powder and the preparation method of dysprosium-silicon synergy | |
| CN110591711B (en) | Gallate red fluorescent powder for white light LED and preparation method thereof | |
| CN104109536B (en) | Oxynitride luminescent material, preparation method and the LED light source be made up of it | |
| CN106753346B (en) | Nitrogen oxides fluorophor and its luminescent device | |
| WO2011044720A1 (en) | Bismuth ion sensitized rare earth germanate luminescence materials and preparation methods thereof | |
| CN101760191B (en) | High-brightness barium-silicate-based blue-green fluorescent powder for LED and high-temperature reducing preparation method thereof | |
| CN110527508A (en) | A kind of nitride red fluorescent powder for white light LED and preparation method thereof | |
| CN111647405B (en) | Green fluorescent powder with rare earth-free double perovskite structure and preparation method thereof | |
| CN114410302A (en) | Near-infrared fluorescent powder and optical device thereof | |
| CN104327852B (en) | Silicon/germinate phosphor, preparation method and application thereof | |
| CN105238401B (en) | White emitting fluorescent powder based on ultraviolet light or near ultraviolet excitation and preparation method thereof | |
| CN102337122A (en) | Silicate green fluorescent powder and preparation method thereof | |
| CN105838371A (en) | Nitric oxide fluorescent powder for LED and preparation method | |
| CN108659841A (en) | A kind of fluorescent powder and preparation method thereof and luminescent device | |
| CN106433623B (en) | A kind of silicon-based nitrogen oxide fluorescent powder and its preparation method and application | |
| CN110283588A (en) | A kind of illumination display phosphor for white light LED and its preparation and application | |
| CN108690618A (en) | A kind of fluorescent powder and preparation method thereof and luminescent device | |
| CN109943324A (en) | A kind of ultra-wide white light phosphor and its preparation method and application and luminaire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |