CN112500860A - Multi-metal modified activated aluminum phosphate luminescent material and preparation method and application thereof - Google Patents
Multi-metal modified activated aluminum phosphate luminescent material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 73
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000002184 metal Substances 0.000 title description 4
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 159000000009 barium salts Chemical class 0.000 claims abstract description 7
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 6
- 230000008635 plant growth Effects 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 56
- 238000000227 grinding Methods 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000005284 excitation Effects 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 17
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 16
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 16
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011656 manganese carbonate Substances 0.000 claims description 14
- 235000006748 manganese carbonate Nutrition 0.000 claims description 14
- 229940093474 manganese carbonate Drugs 0.000 claims description 14
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 14
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical group [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical group O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical group [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 229940099594 manganese dioxide Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 150000004645 aluminates Chemical class 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 239000012190 activator Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 159000000003 magnesium salts Chemical class 0.000 abstract 1
- 150000002696 manganese Chemical class 0.000 abstract 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 24
- 238000000295 emission spectrum Methods 0.000 description 18
- 229910052749 magnesium Inorganic materials 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 238000005245 sintering Methods 0.000 description 14
- 239000003814 drug Substances 0.000 description 13
- 229940079593 drug Drugs 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 238000000695 excitation spectrum Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- -1 rare earth ion Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 229910015999 BaAl Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910003668 SrAl Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LYSCPVVGYLJURL-UHFFFAOYSA-K [O-]P([O-])([O-])=O.OP(O)(O)=O.[Al+3].P Chemical compound [O-]P([O-])([O-])=O.OP(O)(O)=O.[Al+3].P LYSCPVVGYLJURL-UHFFFAOYSA-K 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals
- C09K11/717—Aluminates; Silicates
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
- A01G7/04—Electric or magnetic or acoustic treatment of plants for promoting growth
- A01G7/045—Electric or magnetic or acoustic treatment of plants for promoting growth with electric lighting
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- 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
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Abstract
The invention discloses a polymetallic modified activated aluminum phosphate luminescent material, and a preparation method and application thereof, and belongs to the technical field of luminescent materials. The chemical composition of the compound is MAL12‑x‑y(PO4)0.1O18.85:xMn4+,yMg2+(M is Ca, Sr, Ba or Zn, x is more than or equal to 0.001 and less than or equal to 0.15, and y is more than or equal to 0 and less than or equal to 1.0). The invention is prepared by taking aluminate and phosphate as raw materials, taking calcium salt, strontium salt, barium salt and zinc salt as modified metal ions, taking manganese salt as an activator, taking magnesium salt as a charge compensation agent and adopting an improved high-temperature solid phase method. The preparation method has the advantages of easily available raw materials, simple process, convenient operation, low cost and environmental protection, and the prepared sample emits lightExcellent performance, high color purity and good stability. The aluminum phosphate luminescent material can be widely applied to lighting and display devices and plant growth light-emitting diodes, and is a red luminescent material with a prospect.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and relates to a multi-metal modified activated aluminum phosphate luminescent material, and a preparation method and application thereof.
Background
White LEDs are favored by researchers due to their advantages of high efficiency, long lifetime, good material stability, and environmental friendliness, and are considered to be the best choice for replacing conventional solid state lighting. Currently, commercial W-LEDs combine a blue LED chip with a yellow phosphor YAG: Ce3+But due toThe LED lamp has the defects of lack of red light components, high color temperature, low color rendering index and the like, and greatly restricts the popularization and application of LED illumination. The red fluorescent powder is used as a component for forming the warm white LED fluorescent powder, so that the color temperature can be reduced, and the use comfort level is improved. Therefore, the development of the red luminescent material with excellent performance and good stability has important significance for improving the performance of the W-LED device.
In recent years, Mn is used4+The doped phosphor has excellent spectral performance and strong deep red emission, attracts great attention, can improve the color rendering property and the luminous efficiency of a white light emitting diode, and is used as a luminescent ion in a plurality of inorganic luminescent materials. Meanwhile, the aluminate and phosphate matrixes have stable physical and chemical properties, easily obtained raw materials, low price and mild synthesis conditions.
At present, Mn is a transition metal ion4+A series of studies have been made on the synthesis of doped titanates, aluminates, perovskites, etc., but with regard to the modification of Mn by multi-metal ions4+Few reports of activated aluminophosphate systems exist, and the problems of low luminous efficiency and poor thermal stability still exist in the existing research.
Disclosure of Invention
The present invention is directed to overcoming the problems of Mn in the prior art as described above4+The doped luminescent material has the defects of low luminous efficiency and poor thermal stability, and provides the multi-metal ion modified Mn4+An activated aluminum phosphate luminescent material, a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
multi-metal ion modified Mn4+The activated aluminum phosphate luminescent material has the chemical general formula: MAl12-x-y(PO4)0.1O18.85:xMn4+,yMg2+Wherein x is more than or equal to 0.001 and less than or equal to 0.15, and y is more than or equal to 0 and less than or equal to 1.0; m is any one of Ca, Sr, Ba and Zn.
Preferably, the aluminophosphate luminescent material shows fluorescence intensity of 10 within the range of 600-750 nm under the excitation of ultraviolet light or blue light4～106The deep red color of (a) emits light.
A preparation method of the aluminum phosphate luminescent material comprises the following steps:
1) weighing raw materials according to the stoichiometric ratio of each element in the chemical formula of claim 1, and mixing and grinding the raw materials to obtain a mixture; the raw material comprises Mn4+Compound of (2), containing Mg2+Compound of (2) and containing Al3+And compounds containing P5+The compound of (1), further comprising a calcium salt, a strontium salt, a barium salt or a zinc salt;
2) treating the mixture obtained in the step 1) by using a high-temperature solid phase method, cooling and uniformly grinding to obtain the multi-metal ion modified and activated aluminum phosphate luminescent material.
Preferably, said Mn is contained in step 1)4+The compound of (b) is any one of manganese carbonate, manganese dioxide and manganese acetate; said compound containing Mg2+The compound of (1) is magnesium oxide or magnesium fluoride; said compound containing A13+The compound of (A) is one or more of aluminum oxide, aluminum hydroxide or aluminum nitrate; said compound containing P5+The compound of (1) is ammonium dihydrogen phosphate or phosphoric acid; the calcium salt is calcium carbonate or calcium oxide; the strontium salt is strontium carbonate or strontium nitrate; the barium salt is barium carbonate or barium nitrate; the zinc salt is zinc carbonate, zinc nitrate or zinc oxide.
Preferably, absolute ethyl alcohol and boric acid are added in the grinding process in the step 1); wherein the mass of the absolute ethyl alcohol is 0.5-5 times of the total mass of the raw material mixture, and the mass of the boric acid is 2-30 times of the mass of the x.
Preferably, the grinding time in the step 1) is 0.5-1 h.
Preferably, the high-temperature solid phase method in the step 2) comprises a calcination process, wherein the calcination temperature is 1300-1500 ℃, and the calcination time is 3-5 hours.
Preferably, the specific operation of step 2) is: heating the mixture obtained in the step 1) at room temperature at 5 ℃/min for 80-100 min, heating at 1 ℃/min to 1300-1500 ℃, then carrying out high-temperature calcination, and cooling to room temperature at 2 ℃/min after the calcination is finished to obtain the multi-metal ion modified Mn4+Activated aluminophosphate hairAn optical material.
The application of the aluminum phosphate luminescent material in preparing the plant growth light-emitting diode is characterized in that the aluminum phosphate luminescent material is sprayed on the inner wall of the light-emitting diode.
The application of the aluminum phosphate luminescent material in preparing LED lighting equipment and LED display devices is characterized in that the aluminum phosphate luminescent material is sprayed on the inner wall of the LED lighting equipment or the LED display devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a multi-metal modified Mn4+Activated aluminophosphate luminescent materials having a chemical composition of MAl12-x-y(PO4)0.1O18.85:xMn4+,yMg2+Wherein M is Ca, Sr, Ba or Zn, x is more than or equal to 0.001 and less than or equal to 0.15, and y is more than or equal to 0 and less than or equal to 1.0. Mn4 +Is a luminescent center, Mg2+Is a charge compensator. Transition metal ion Mn4+Having a 3d3An electronic structure capable of generating a wide excitation band from ultraviolet to blue light, and is combined with A13+The ionic radii are similar, so Al-O in aluminate6Has a strong Mn-accepting octahedral coordination structure4+The ability to substitute. The aluminate and phosphate matrix materials have the advantages of excellent chemical stability and thermal stability, low price, environmental protection and the like, generally show wide and strong absorption between 300 and 500nm and deep red emission between 600 and 750nm according to corresponding local crystal field environments, and have good thermal stability and high brightness. Namely, the multi-metal ion modified and activated aluminum phosphate luminescent material has good luminescent performance, high brightness, good stability and good color purity under the excitation of ultraviolet light or blue light.
The invention also discloses a preparation method of the multi-metal ion modified activated aluminum phosphate luminescent material, which takes an aluminum phosphate system as a substrate, namely, takes Al-containing3+Compound of (1), containing Ca2+Compound of (5) containing Sr2+Compound of (1), containing Zn2+Compound of (5) containing Ba2+And compounds containing P5+Is used as raw material and doped with Mn4+As activators, compounds containing Mg2+The compound of (1) is used as a charge compensation agent. In the presence of Mn as a transition metal4+The rare earth ion is replaced, and the preparation is carried out by adopting a high-temperature solid phase method. The invention utilizes the synergistic effect to lead the spectrum of the luminescent material to generate red shift by changing the metal ions in the matrix, thereby influencing the performance of the luminescent material, obviously improving the luminous efficiency and the thermal stability of the luminescent material, and simultaneously using transition metal ions Mn4+Replaces rare earth ions and reduces the production cost. Namely, the preparation method of the invention has the advantages of easily available raw materials, simple process, convenient operation, low cost and environmental protection.
Further, absolute ethyl alcohol and boric acid are added in the grinding process, and the absolute ethyl alcohol is beneficial to uniform grinding and refining of the sample. When H is added3BO3During the process, a small amount of boron-rich liquid phase is generated in the sample at high temperature, and the boron-rich liquid phase is beneficial to increasing the mutual contact between the raw materials and improving the purity and the crystallization degree of the sample.
Further, the Mn is contained4+The compound of (b) is any one of manganese carbonate, manganese dioxide and manganese acetate; said compound containing A13+The compound of (A) is one or more of aluminum oxide, aluminum hydroxide or aluminum nitrate; said Ca-containing2+The compound of (b) is calcium oxide or calcium carbonate; said compound containing P5+The compound of (1) is ammonium dihydrogen phosphate or phosphoric acid. Under the condition of ensuring similar and reasonable physical properties, the influence of calcium salt, strontium salt, barium salt and zinc salt in the matrix can be explained by changing the calcium salt, the strontium salt, the barium salt and the zinc salt.
The multi-metal ion modified activated aluminum phosphate luminescent material is a red luminescent material with a prospect, and can be sprayed on the inner wall of a light-emitting diode to prepare a plant growth light-emitting diode. Meanwhile, the aluminum phosphate luminescent material can be widely applied to lighting equipment and display devices, and is particularly suitable for Mn4+Ion-based white LEDs.
Drawings
FIG. 1 is a CaAl prepared according to example 1 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+X-ray diffraction pattern of red fluorescent powder;
FIG. 2 is a CaAl prepared according to example 1 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+(a) The graph is an emission spectrum of red fluorescent powder under the excitation of light with 396 nm; (b) the graph is a graph of the excitation spectrum under monitoring of light at 654 nm;
FIG. 3 is a CaAl prepared according to example 1 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+An emission spectrum of the red fluorescent powder at different temperatures excited by 396 nm; (a) the graph is an emission spectrum corresponding to the temperature 298-383K, and the (b) graph is an emission spectrum corresponding to the temperature 413-533K;
FIG. 4 is a CaAl prepared according to example 1 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+A color coordinate change diagram of the red fluorescent powder in the temperature range of 298-383K excited at 396 nm;
FIG. 5 shows CaAl prepared according to example 1 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+The quantum efficiency of the phosphor synthesized by the red phosphor under the excitation of 396nm is calculated to be 78%.
FIG. 6 shows SrAl prepared according to example 2 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+X-ray diffraction pattern of red fluorescent powder;
FIG. 7 shows SrAl prepared in example 2 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+(a) The graph is an emission spectrum of red fluorescent powder under the excitation of light at 397 nm; (b) the graph is a graph of the excitation spectrum under monitoring with 657nm light;
FIG. 8 shows ZnAl production according to the invention in example 311.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+X-ray diffraction of red phosphorShooting a map;
FIG. 9 is a ZnAl alloy prepared according to example 3 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+(a) The graph is an emission spectrum of red fluorescent powder under 467nm light excitation; (b) FIG. is a graph of excitation spectra under 676nm light monitoring;
FIG. 10 shows BaAl prepared according to example 4 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+X-ray diffraction pattern of red fluorescent powder;
FIG. 11 is BaAl prepared according to example 4 of the present invention11.89(PO4)0.1O18.85:0.01Mn4+，0.1Mg2+(a) The graph is an emission spectrum of red fluorescent powder under the excitation of light with 468 nm; (b) the graph is a graph of the excitation spectrum under light monitoring at 700 nm;
FIG. 12 shows four different metal ions (Ca) according to examples 1, 2, 3 and 4 of the present invention2+,Sr2+,Zn2+,Ba2+) Color coordinates of the modified red phosphor;
FIG. 13 CaAl prepared according to example 5 of the invention11.99-y(PO4)0.1O18.85:0.01Mn4+，yMg2+And (y is 0,0.1,0.2,0.3,0.4 and 0.6) the emission spectrum of the series of samples under the excitation of 396nm light.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+0.1000g of calcium carbonate, 0.0012g of manganese carbonate, 0.0062g of magnesium fluoride, 0.9274g of aluminum hydroxide and 0.0115g of ammonium dihydrogen phosphate are weighed according to the stoichiometric ratio of Ca, Al, P, Mn and Mg in (M ═ Ca), the raw materials are mixed and placed in an agate mortar, 2ml of absolute ethyl alcohol is added and then ground, the obtained mixture is placed in a muffle furnace and calcined in the air atmosphere, the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, taking out a sample, grinding, and sealing for later use to obtain Ca2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
With Ca from example 12+The experiment verification is carried out by taking the ion-modified activated aluminum phosphate luminescent material as an example, and the result is as follows:
for Ca prepared in example 12+The ion-modified activated aluminum phosphate luminescent material is subjected to performance characterization, the X-ray diffraction pattern result is shown in figure 1, and the XRD test result shows that Ca prepared in example 12+Ion-modified Mn4+The activated aluminum phosphate luminescent material has better crystallinity and is a pure phase material.
The emission spectrum under 396nm excitation is shown in FIG. 2(a), which shows three distinct peaks at 641nm, 654nm and 664 nm. The peak emission at 654nm is Mn4+Is/are as follows2E→4A2Transition, and shoulders at 642 and 664nm belong to2E→4A2The emission spectrum of the phonon subband shows that the main peak is positioned at 654nm and pure red light is obtained.
The excitation spectrum was monitored at a wavelength of 654nm, and the result is shown in FIG. 2(b), in which there are three peaks, i.e., excitation bands at 343nm, 396nm and 467nm, respectively, and Mn at 343nm and 467nm, respectively4+Is/are as follows4A2→4T1And4A2→4T2transition and Mn at 396nm4+Is/are as follows4A2→2T2The transition is emitted. The results show that the red phosphor is effectively excited in the ultraviolet region and the blue region.
Emission at different temperatures with 396nm excitationThe spectrum and the results are shown in FIG. 3. It can be seen that the shape and position of the characteristic peak of the emission spectrum did not significantly change, but the emission intensity gradually decreased with increasing temperature, indicating that2The E excited state undergoes a gradual non-radiative transition with increasing temperature. When the temperature is raised to 413K, the fluorescence intensity is still 60% of the initial intensity, which indicates that the fluorescent powder has good thermal stability.
FIG. 4 shows the color coordinate change of the phosphor in the temperature range of 298K-533K, and the results in FIG. 4 show that the difference between the color coordinates x and y is 0.0089 and 0.0088, respectively, which indicates that the color coordinate change of the synthesized phosphor in 298K-533K is very small, and the synthesized phosphor has better color stability.
The quantum efficiency of the synthesized phosphor under the excitation of 396nm was measured according to the four-curve method, and the result is shown in fig. 5, and the quantum efficiency of the phosphor was calculated to be 80% according to fig. 5, indicating that the aluminophosphate luminescent material has higher luminous efficiency.
Example 2
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+0.1476g of strontium carbonate, 0.0012g of manganese carbonate, 0.0062g of magnesium fluoride, 0.9274g of aluminum hydroxide and 0.0115g of ammonium dihydrogen phosphate are weighed according to the stoichiometric ratio of Sr, Al, P, Mn and Mg in (M ═ Sr). The weighed medicines are mixed and placed in an agate mortar, 2ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace to be calcined in the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Sr2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
With Sr of example 22+Ion-modified Mn4+The activated aluminum phosphate luminescent material is taken as an example for experimental verification, and the result is as follows:
sr prepared in example 22+The ion modified activated aluminum phosphate luminescent material is subjected to performance characterization, the X-ray diffraction pattern result is shown in figure 6, and the XRD test result shows that Sr prepared in example 22+Ion-modified aluminophosphate red fluorescenceThe light powder has better crystallinity and is a pure phase material.
The result of the emission spectrum under 397nm excitation is shown in FIG. 7(a), which shows three distinct peaks at 643nm, 657nm and 669 nm. 657nm peak emission belongs to Mn4+Is/are as follows2E→4A2Transitions, and shoulders at 643 and 669nm belong to2E→4A2The emission spectrum of the phonon subband shows that the main peak is positioned at 657nm of red light with pure chroma.
The excitation spectrum was monitored at a wavelength of 657nm, and the results are shown in FIG. 7(b), in which there were three peaks, i.e., excitation bands at 344nm, 397nm and 467nm, respectively, and Mn at 344nm and 467nm, respectively4+Is/are as follows4A2→4T1And4A2→4T2transition, and belongs to Mn at 397nm4+Is/are as follows4A2→2T2The transition is emitted. The results show that the red phosphor prepared in this example is excited effectively in the ultraviolet region and the blue region.
Example 3
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+0.1254g of zinc carbonate, 0.0012g of manganese carbonate, 0.0062g of magnesium fluoride, 0.9274g of aluminum hydroxide and 0.0115g of ammonium dihydrogen phosphate are weighed according to the stoichiometric ratio of Zn, Al, P, Mn and Mg in (M ═ Zn). The weighed medicines are mixed and placed in an agate mortar, 3ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace to be calcined in the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Zn2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
With the Zn of example 32+Ion-modified Mn4+The activated aluminum phosphate luminescent material is taken as an example for experimental verification, and the result is as follows:
zn prepared in example 32+Ion-modified Mn4+The activated aluminophosphate luminescent materials were subjected to performance characterization by X-ray diffractionThe pattern results are shown in FIG. 8, which shows the Zn prepared in example 3 by XRD test2+Ion-modified Mn4+The activated aluminum phosphate luminescent material has better crystallinity and is a pure phase material.
The emission spectrum under 467nm excitation showed a distinct peak at 676nm in FIG. 9(a), which is attributed to Mn4+Is/are as follows2E→4A2Transition, and the shoulder at 692nm belongs to2E→4A2The emission spectrum of the phonon subband shows that the main peak is positioned at 676nm red light with pure chroma.
The excitation spectrum was monitored at a wavelength of 676nm, and the result is shown in FIG. 9(b), in which a distinct peak was observed at 467nm, which is attributed to Mn4+Is/are as follows4A2→4T2And (4) transition. The results show that the red phosphor is efficiently excited in the blue region.
Example 4
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+In the stoichiometric ratio of Ba, Al, P, Mn, and Mg in (M ═ Ba), 0.1973g of barium carbonate, 0.0012g of manganese carbonate, 0.0062g of magnesium fluoride, 0.9274g of aluminum hydroxide, and 0.0115g of ammonium dihydrogen phosphate were weighed. The weighed medicines are mixed and placed in an agate mortar, 3ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace to be calcined in the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Ba2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
With Ba of example 42+Ion-modified Mn4+The activated aluminum phosphate luminescent material is taken as an example for experimental verification, and the result is as follows:
ba prepared in example 42+The ion-modified activated aluminum phosphate luminescent material is subjected to performance characterization, the X-ray diffraction pattern result is shown in figure 10, and the XRD test result shows that the Ba prepared in example 42+The ion-modified red aluminum phosphate phosphor has better crystallinityAnd is a pure phase material.
The emission spectrum under 468nm excitation is shown in FIG. 11(a), which shows two distinct peaks at 634nm and 700nm, respectively. The peak emission at 700nm is Mn4+Is/are as follows2E→4A2Transition, and the peak of 634 belongs to2E→4A2The emission spectrum of the phonon subband shows that the main peak is positioned at 700nm and the chroma of red light is pure.
The result of the excitation spectrum under 700nm wavelength monitoring is shown in FIG. 11(b), in which a distinct peak at 468nm is observed due to Mn4+Is/are as follows4A2→4T2And (4) transition, wherein the result shows that the red fluorescent powder is effectively excited in a blue light region.
Four different metal ions (Ca) were used in examples 1, 2, 3 and 42+,Sr2+,Zn2+,Ba2+) The color coordinates of the modified activated aluminophosphate luminescent material were compared, and as a result, as shown in fig. 12, by comparison with the above 3 examples, it was found that the wavelength was gradually red-shifted in the visible region.
Example 5
According to MAL11.99-y(PO4)0.1O18.85:0.01Mn4+,yMg2+The stoichiometric ratio of Ca, Al, P, Mn and Mg in (M ═ Ca, y ═ 0,0.1,0.2,0.3,0.4,0.6) is respectively measured, 0.1000g of calcium carbonate, 0.002g of manganese carbonate and 0.0115g of ammonium dihydrogen phosphate are respectively measured, then 0g of magnesium fluoride, 0.0062g, 0.0124g, 0.0186g, 0.0248g and 0.0372g are respectively measured, 0.9355g, 0.9274g, 0.9196g, 0.9118g, 0.904g and 0.8884g are respectively measured, the weighed medicines are mixed according to the corresponding numbers and placed in an agate mortar, 3ml of absolute ethyl alcohol is added and then grinding is carried out, and six mixtures obtained are placed in a muffle furnace under the air atmosphere for calcination, the calcination temperature is 1450 ℃, and the calcination time is 4 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain six kinds of Ca2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
CaAl prepared in this example11.99-y(PO4)0.1O18.85:0.01Mn4+,yMg2+The emission spectrum of the (y-0, 0.1,0.2,0.3,0.4,0.6) series of samples under the excitation of 396nm light is shown in fig. 13. With Mg2+The position of the main peak of the emission line is not changed when the doping concentration is increased, but the luminous intensity of the sample is obviously changed, and the intensity of the luminous intensity is changed along with Mg2+The concentration increases, and when y is 0.1, the emission intensity of the sample reaches the maximum, and then the emission intensity decreases with the increase of the doping concentration, and a concentration quenching phenomenon occurs.
Example 6
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.2Mg2+In the stoichiometric ratio of Sr, Al, P, Mn and Mg in (M ═ Sr), 0.21164g of strontium nitrate, 0.0012g of manganese carbonate, 0.0124g of magnesium fluoride, 0.9274g of aluminum hydroxide and 0.0115g of ammonium dihydrogen phosphate are weighed respectively. The weighed medicines are respectively numbered, mixed and placed in an agate mortar, 4ml of absolute ethyl alcohol is added for grinding, and the obtained mixture is placed in a muffle furnace for calcination under the air atmosphere, wherein the calcination temperature is 1300 ℃, and the calcination time is 5 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Sr2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 7
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+In the stoichiometric ratio of Zn, Al, P, Mn, and Mg in (M ═ Zn), 0.1254g of zinc nitrate, 0.0009g of manganese dioxide, 0.0062g of magnesium fluoride, 0.9274g of aluminum hydroxide, and 0.0115g of ammonium dihydrogen phosphate were weighed. The weighed medicines are mixed and placed in an agate mortar, 2ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace to be calcined in the air atmosphere, wherein the calcination temperature is 1400 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Zn2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 8
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+In the stoichiometric ratio of Ba, Al, P, Mn, and Mg in (M ═ Ba), 0.0261g of barium nitrate, 0.0009g of manganese dioxide, 0.0062g of magnesium fluoride, 0.9274g of aluminum hydroxide, and 0.0115g of ammonium dihydrogen phosphate were weighed, respectively. The weighed medicines are mixed and placed in an agate mortar, 3ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace to be calcined in the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Ba2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 9
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+In the stoichiometric ratio of Ca, Al, P, Mn, and Mg in (M ═ Ca), 0.1000g of calcium carbonate, 0.0012g of manganese carbonate, 0.0062g of magnesium fluoride, 0.9274g of aluminum hydroxide, and 0.0098g of phosphoric acid were weighed, respectively. The weighed medicines are mixed and placed in an agate mortar, 2ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace for calcination under the air atmosphere, wherein the calcination temperature is 1300 ℃, and the calcination time is 4 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Ca2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 10
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+In the stoichiometric ratio of Zn, Al, P, Mn, and Mg in (M ═ Zn), 0.0814g of zinc oxide, 0.0012g of manganese carbonate, 0.0124g of magnesium fluoride, 0.9274g of aluminum hydroxide, and 0.0115g of ammonium dihydrogen phosphate were weighed, respectively. The weighed medicines are mixed and placed in an agate mortar, 2ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace for calcination under the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Zn2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 11
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+In the stoichiometric ratio of Ca, Al, P, Mn, and Mg in (M ═ Ca), 0.056g of calcium oxide, 0.0012g of manganese carbonate, 0.0124g of magnesium fluoride, 0.9274g of aluminum hydroxide, and 0.0115g of ammonium dihydrogen phosphate were weighed, respectively. The weighed medicines are mixed and placed in an agate mortar, 2ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace for calcination under the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Ca2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 12
According to MAL11.89(PO4)0.1O18.85:0.01Mn4+,0.1Mg2+In the stoichiometric ratio of Sr, Al, P, Mn and Mg in (M ═ Sr), 0.1476g of strontium carbonate, 0.0017g of manganese acetate, 0.0124g of magnesium fluoride, 0.9274g of aluminum hydroxide and 0.0115g of ammonium dihydrogen phosphate were weighed. The weighed medicines are mixed and placed in an agate mortar, 3ml of absolute ethyl alcohol is added and then ground, and the obtained mixture is placed in a muffle furnace for calcination under the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 3 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain Sr2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 13
According to MAL11.99-y(PO4)0.1O18.85:0.01Mn4+,yMg2+In the stoichiometric ratio of Ca, Al, P, Mn and Mg in (M ═ Ca, y ═ 0.7,0.8,0.9,1.0), 0.1000g of calcium carbonate, 0.002g of manganese carbonate, 0.0115g of ammonium dihydrogen phosphate, 0.0434g of magnesium fluoride, 0.0496g, 0.0558g, 0.062g of magnesium fluoride, 0.8806g of aluminum hydroxide, 0.8728g, 0.8650g and 0.8572g of magnesium were weighed, respectively. Mixing the weighed medicines according to corresponding sequence numbers, placing the mixture into an agate mortar, adding 5ml of absolute ethyl alcohol, grinding, placing the obtained four mixtures into a muffle furnace to calcine under the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination temperature isThe time is 4 h. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain four kinds of Ca2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
Example 14
According to MAL11.9-x(PO4)0.1O18.85:xMn4+,0.1Mg2+In the stoichiometric ratio of Ca, Al, P, Mn and Mg in (M ═ Ca, x ═ 0.001,0.15), 0.1000g of calcium carbonate, 0.0062g of magnesium fluoride, 0.0115g of ammonium dihydrogen phosphate, 0.0001g and 0.0173g of manganese carbonate, 0.9281g and 0.9165g of aluminum hydroxide were weighed, respectively. The weighed medicines are mixed according to the corresponding serial numbers and placed in an agate mortar, 4ml of absolute ethyl alcohol is added and then ground, and the obtained two mixtures are placed in a muffle furnace to be calcined under the air atmosphere, wherein the calcination temperature is 1450 ℃, and the calcination time is 4 hours. After calcining and sintering, naturally cooling to room temperature, and grinding uniformly to obtain two kinds of Ca2+Ion-modified Mn4+An activated aluminophosphate luminescent material.
In conclusion, the metal ion modified aluminum phosphate red fluorescent powder prepared by the invention has good luminous performance, high brightness, good stability and high color purity under the excitation of ultraviolet light or blue light. And the preparation method has the advantages of easily available raw materials, simple process, convenient operation, low cost and environmental protection. The aluminum phosphate luminescent material is sprayed on the inner wall of the light-emitting diode, so that the plant growth light-emitting diode can be prepared. Meanwhile, the aluminum phosphate luminescent material can be widely applied to lighting equipment and display devices, and is particularly suitable for Mn4+Ion-based white LEDs.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. Multi-metal ion modified Mn4+An activated aluminophosphate luminescent material, wherein the phosphor has the chemical formula: MAl12-x-y(PO4)0.1O18.85:xMn4+,yMg2+Wherein x is more than or equal to 0.001 and less than or equal to 0.15, and y is more than or equal to 0 and less than or equal to 1.0; m is any one of Ca, Sr, Ba and Zn.
2. The aluminophosphate luminescent material according to claim 1, wherein the aluminophosphate luminescent material exhibits a fluorescence intensity of 10 in a range of 600 to 750nm under excitation of ultraviolet light or blue light4～106The deep red color of (a) emits light.
3. A method for preparing an aluminophosphate luminescent material as defined in claim 1 or 2, comprising the steps of:
1) weighing raw materials according to the stoichiometric ratio of each element in the chemical formula of claim 1, and mixing and grinding the raw materials to obtain a mixture; the raw material comprises Mn4+Compound of (2), containing Mg2+Compound of (2) and containing Al3+And compounds containing P5+The compound of (1), further comprising a calcium salt, a strontium salt, a barium salt or a zinc salt;
2) treating the mixture obtained in the step 1) by using a high-temperature solid phase method, cooling and uniformly grinding to obtain the multi-metal ion modified and activated aluminum phosphate luminescent material.
4. The method according to claim 3, wherein the Mn-containing compound of step 1)4+The compound of (b) is any one of manganese carbonate, manganese dioxide and manganese acetate; said compound containing Mg2+The compound of (1) is magnesium oxide or magnesium fluoride; said compound containing A13+The compound of (A) is one or more of aluminum oxide, aluminum hydroxide or aluminum nitrate; said compound containing P5+The compound of (1) is ammonium dihydrogen phosphate or phosphoric acid; the calcium salt is calcium carbonate or calcium oxide; the strontium salt is strontium carbonate or strontium nitrate; the barium salt is barium carbonate or barium nitrate; the zinc salt is zinc carbonate, zinc nitrate or zinc oxide.
5. The method according to claim 3, wherein absolute ethanol and boric acid are added during the milling in step 1); wherein the mass of the absolute ethyl alcohol is 0.5-5 times of the total mass of the raw material mixture, and the mass of the boric acid is 2-30 times of the mass of the x.
6. The preparation method according to claim 3, wherein the grinding time in step 1) is 0.5-1 h.
7. The preparation method of claim 3, wherein the high-temperature solid phase method in the step 2) comprises a calcination process, wherein the calcination temperature is 1300-1500 ℃, and the calcination time is 3-5 h.
8. The preparation method according to claim 7, wherein the specific operation of step 2) is: heating the mixture obtained in the step 1) at room temperature at 5 ℃/min for 80-100 min, heating at 1 ℃/min to 1300-1500 ℃, then carrying out high-temperature calcination, and cooling to room temperature at 2 ℃/min after the calcination is finished to obtain the multi-metal ion modified Mn4+An activated aluminophosphate luminescent material.
9. Use of an aluminophosphate luminescent material as claimed in claim 1 or 2 in the manufacture of a plant growth light emitting diode, characterised in that the aluminophosphate luminescent material is sprayed onto the inner wall of the light emitting diode.
10. Use of the aluminophosphate luminescent material according to claim 1 or 2 for the production of LED lighting devices and LED display devices, wherein the aluminophosphate luminescent material is sprayed onto the inner walls of LED lighting devices or LED display devices.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201341A (en) * | 2021-05-14 | 2021-08-03 | 陕西科技大学 | Alkali metal charge compensation type aluminum phosphate red luminescent material and preparation method and application thereof |
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