CN117070215A - Phosphate near-infrared luminescent material and preparation method and application thereof - Google Patents
Phosphate near-infrared luminescent material and preparation method and application thereof Download PDFInfo
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- CN117070215A CN117070215A CN202311039590.4A CN202311039590A CN117070215A CN 117070215 A CN117070215 A CN 117070215A CN 202311039590 A CN202311039590 A CN 202311039590A CN 117070215 A CN117070215 A CN 117070215A
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 35
- 239000010452 phosphate Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims description 52
- 239000010955 niobium Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 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 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- ZIRLXLUNCURZTP-UHFFFAOYSA-I tantalum(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Ta+5] ZIRLXLUNCURZTP-UHFFFAOYSA-I 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 11
- 238000001228 spectrum Methods 0.000 abstract description 6
- 230000005284 excitation Effects 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 238000000295 emission spectrum Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004297 night vision Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- 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
- C09K11/7709—Phosphates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the technical field of luminescent materials, and discloses a phosphate near-infrared luminescent material, a preparation method and application thereof. The chemical formula of the material is M 1 0.5‑x M 2 0.5 Cr x P 2 O 7 ；M 1 At least one selected from Al, ga, in or Sc, M 2 Selected from Ta and/or Nb, x is more than or equal to 0.001 and less than or equal to 0.2,0.001 and x is more than or equal to 0.2. The luminescent material realizes fine regulation and control of luminescence peak position and luminescence efficiency by adjusting the proportion between Ta/Nb and Al/Ga/Sc/In, can be efficiently excited by blue light with the wave band of 440-480nm, has the emission peak wavelength of 840-900 nm and can be continuously changed, has higher relative luminescence intensity, and can effectively meet the requirements of wide-spectrum near-infrared LED devices.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a phosphate near-infrared luminescent material, and a preparation method and application thereof.
Technical Field
Near infrared light is widely used in the fields of food detection, biomedical imaging, medical diagnosis, face recognition, night vision technology and the like. However, conventional near infrared light sources, such as halogen lamps, incandescent lamps, and the like, generally suffer from low efficiency, short life, large volume, large power consumption, and the like. Although the infrared LED has small volume and low power consumption, the infrared LED has narrower emission spectrum, can not cover a larger spectrum range and is limitedIt finds application in many fields. In recent years, near infrared LEDs based on luminescence conversion have advantages of small size, high efficiency, long service life, adjustable spectrum, and the like, and are considered as a new generation of near infrared light sources. Therefore, development of the efficient near infrared luminescent material has important application prospect. Typically, cr 3+ And Eu 2+ Activator ions selected as broad spectrum near infrared luminescent materials, but Eu 2+ The emission wavelength of the activated near infrared material is difficult to break through 830nm, and the luminous efficiency is generally low; while Cr 3+ The light-emitting peak wavelength of the activated near infrared light-emitting material is adjustable between 750 and 1100nm, and the light-emitting efficiency of the activated near infrared light-emitting material can tend to be 100% in the wave band of 750 to 830nm, so that Cr 3+ Activated near infrared luminescent material development is currently the mainstream. Unfortunately, however, cr 3+ The activated near-infrared luminescent material has a decreasing trend in luminous efficiency with increasing wavelength due to the dependence on a weak crystal field, so that the quantity of materials with peak wavelength larger than 830nm band is small and the efficiency is low. Therefore, the method for exploring and developing the high-efficiency near-infrared luminescent material with the peak wavelength larger than 830nm has important application value.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a phosphate near-infrared luminescent material, which can realize fine regulation and control of luminescence peak position and luminescence efficiency by adjusting the proportion between Ta/Nb and Al/Ga/Sc/In, can be efficiently excited by blue light with the wave band of 440-480nm, has the emission peak wavelength of 840-900 nm and can be continuously changed, has higher relative luminescence intensity, and can effectively meet the requirements of a wide-spectrum near-infrared LED device.
Another object of the present invention is to provide a method for preparing the above-mentioned phosphate near infrared luminescent material.
It is a further object of the present invention to provide the use of the above-described phosphate near infrared luminescent material.
The aim of the invention is achieved by the following technical scheme:
a phosphate near infrared luminescent material with a chemical formula of M 1 0.5-x Cr x M 2 0.5 P 2 O 7 ；M 1 At least one selected from Al, ga, in or Sc, M 2 Selected from Ta and/or Nb, x is more than or equal to 0.001 and less than or equal to 0.2.
Preferably, the material has the formula M 1 0.5-x Cr x Ta 0.5 P 2 O 7 Or M 1 0.5-x Cr x (Ta,Nb) 0.5 P 2 O 7 Wherein Ta is Nb is more than or equal to 1.
The preparation method of the phosphate near infrared luminescent material comprises the following specific steps:
s1, M is 1 Compounds, M 2 Grinding and mixing the compound, the P compound and the Cr compound uniformly to obtain a mixture;
s2, sintering the mixture in the air at 900-1100 ℃, and crushing and grinding the product to obtain the phosphate near infrared luminescent material.
Preferably, M is as described in step S1 1 The compound is more than one of aluminum oxide, aluminum hydroxide, aluminum nitrate, gallium oxide, indium oxide, scandium oxide or scandium nitrate; the M is 2 The compound is more than one of tantalum oxide, tantalum hydroxide, niobium oxide or niobium hydroxide; the P compound is more than one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate or phosphorus pentoxide; the Cr compound is chromium oxide and/or chromium nitrate.
Preferably, the sintering time in step S2 is 4 to 48 hours.
The phosphate near infrared luminescent material is applied to light conversion devices.
Preferably, the light conversion device is a near infrared LED device.
The invention uses the optical active element Cr 3+ Dissolved in M having cubic structure 1 M 2 P 2 O 7 Compound (M) 1 =al, ga, in, and Sc; m is M 2 =ta or Nb) to obtain a brand new broad spectrum near infrared luminescent material system with excitation peak wavelength covering 440-480nm band and emission peak wavelength at 840-900 nm. Belongs to a compound with a new structure and a new component, and has potential application value. The inventionMing Cr 3+ Separately doping M 1 M 2 P 2 O 7 (M 1 =one or more of Al, ga, in or Sc, M 2 =ta or/and Nb), and on the basis of this, by varying the Ta/Nb and Al/Ga/Sc/In ratios, a new-component luminescent material is formed, comprising a mixture of the above-mentioned components as a main component, but based on the luminescence intensity of the material, when M 2 When Ta is used alone or in combination with Nb, the Ta-containing component has higher luminous intensity, mainly because Ta has weaker electronegativity than Nb and stronger electron supply characteristic, and is favorable for the valence stability of Cr. The phosphate near infrared luminescent material can realize fine regulation and control of luminescence peak position and luminescence efficiency by adjusting the ratio of Ta/Nb and Al/Ga/Sc/In.
Compared with the prior art, the invention has the following beneficial effects:
1. the excitation peak wavelength of the phosphate near infrared luminescent material covers 440-480nm wave band, can be well matched with a blue light LED, and has strong practicability.
2. The phosphate near infrared luminescent material can emit near infrared light with the peak wavelength of about 840-900 nm under the excitation of 460nm blue light, and is a near infrared material which is currently in shortage.
3. The raw materials of the phosphate near infrared luminescent material are cheap and easy to obtain. And the synthesis temperature is lower than that of other oxide systems (such as garnet, spinel and the like), the preparation process is simple, special reaction equipment is not needed, and the industrial production is very convenient.
Drawings
FIG. 1 is Al in example 1 0.48 Cr 0.02 Ta 0.5 P 2 O 7 Is an X-ray powder diffraction pattern of (2);
FIG. 2 is Al in example 1 0.48 Cr 0.02 Ta 0.5 P 2 O 7 Is a single crystal;
FIG. 3 is Al in example 1 0.48 Cr 0.02 Ta 0.5 P 2 O 7 Is a spectrum of the emission spectrum of (a);
FIG. 4 shows Ga in example 2 0.49 Cr 0.01 Ta 0.5 P 2 O 7 Is a single crystal;
FIG. 5 is Ga in example 2 0.49 Cr 0.01 Ta 0.5 P 2 O 7 Is a spectrum of the emission spectrum of (a);
FIG. 6 is In example 3 0.499 Cr 0.001 Ta 0.5 P 2 O 7 Is a single crystal;
FIG. 7 is In example 3 0.499 Cr 0.001 Ta 0.5 P 2 O 7 Is provided.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
According to chemical formula Al 0.48 Cr 0.02 Ta 0.5 P 2 O 7 Weigh 0.024mol of Al 2 O 3 0.001mol of Cr 2 O 3 Ta 0.025mol 2 O 5 And 0.2mol of NH 4 H 2 PO 4 The raw materials are all analytically pure, the raw materials are fully ground for 30min, mixed uniformly, put into an alumina crucible, baked for 6h at 1080 ℃, and after cooling to room temperature, the product is crushed, ground, washed and the like for post-treatment, thus obtaining the phosphate near infrared luminescent material, the chemical composition of which is Al 0.48 Cr 0.02 Ta 0.5 P 2 O 7 。
FIG. 1 is Al in example 1 0.48 Cr 0.02 Ta 0.5 P 2 O 7 Is a powder X-ray diffraction pattern of (C). (Cu target, λ= 0.15406 nm) and Al 0.5 Ta 0.5 P 2 O 7 As can be seen from FIG. 1, the present embodiment successfully produces Al 0.48 Cr 0.02 Ta 0.5 P 2 O 7 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 2 is Al in example 1 0.48 Cr 0.02 Ta 0.5 P 2 O 7 Is measured (at 845 nm); as can be seen from FIG. 2, the luminescent powder can be effectively excited by blue light and red light within the range of 350-800 nm, and the main excitation peak is located at 460nm. FIG. 3 shows Al in the present embodiment 0.48 Cr 0.02 Ta 0.5 P 2 O 7 As can be seen from fig. 3, the emission spectrum covers 700 to 1200nm, and the main emission peak is located at 845nm. The relative luminescence intensity was set to 100% under excitation with 460nm blue light (see table 1).
Example 2
According to chemical formula Ga 0.49 Cr 0.01 Ta 0.5 P 2 O 7 Weigh 0.245mol Ga 2 O 3 、0.01mol Cr(NO 3 ) 3 、0.25mol Ta 2 O 5 And 2mol NH 4 H 2 PO 4 The raw materials are all analytically pure, the raw materials are fully ground for 30min, mixed uniformly, put into an alumina crucible, baked for 10h at 1050 ℃, and after cooling to room temperature, the product is crushed, ground, washed and the like for post-treatment, thus obtaining the phosphate near infrared luminescent material, the chemical composition of which is Ga 0.49 Cr 0.01 Ta 0.5 P 2 O 7 。
FIG. 4 shows Ga in example 2 0.49 Cr 0.01 Ta 0.5 P 2 O 7 Excitation spectrum (at 865 nm); as can be seen from FIG. 4, the luminescent powder can be effectively excited by blue light and red light within the range of 350-770 nm, and the main excitation peak is positioned at 465nm. FIG. 5 shows Ga in the present embodiment 0.49 Cr 0.01 Ta 0.5 P 2 O 7 As can be seen from fig. 5, the emission spectrum covers 700 to 1200nm, and the main emission peak is at 865nm. The relative luminous intensity reached 90% under excitation with 460nm blue light (see table 1).
Example 3
According to the chemical formula In 0.499 Cr 0.001 Ta 0.5 P 2 O 7 0.2495mol of In was weighed 2 O 3 、0.0005mol Cr 2 O 3 、0.25mol Ta 2 O 5 And 2mol NH 4 HPO 4 The above raw materials are all analytically pure, and the above materials are addedGrinding the raw materials for 30min, mixing, placing into an alumina crucible, roasting at 1030 deg.C for 14h, cooling to room temperature, crushing, grinding, washing, etc. to obtain near infrared luminescent material with chemical composition In 0.499 Cr 0.001 Ta 0.5 P 2 O 7 。
FIG. 6 is In example 3 0.499 Cr 0.001 Ta 0.5 P 2 O 7 Is at 880 nm; as can be seen from FIG. 6, the luminescent powder can be effectively excited by blue light and red light in the range of 350-780 nm, and the main excitation peak is located at 470nm. FIG. 7 shows In the present embodiment 0.499 Cr 0.001 Ta 0.5 P 2 O 77 As can be seen from FIG. 7, the emission spectrum covers 700 to 1200nm, and the main emission peak is 880nm. The relative luminous intensity reached 85% under excitation with 460nm blue light (see table 1).
Example 4
According to chemical formula Al 0.465 Cr 0.035 Nb 0.5 P 2 O 7 0.0465mol Al (OH) 3 、0.0175mol Cr 2 O 3 、0.025mol Nb 2 O 5 And 0.2mol NH 4 H 2 PO 4 The raw materials are all analytically pure, the raw materials are fully ground for 30min, mixed uniformly, put into an alumina crucible, baked for 18h at 1000 ℃, and after cooling to room temperature, the product is crushed, ground, washed and the like for post-treatment, thus obtaining the phosphate near infrared luminescent material, the chemical composition of which is Al 0.465 Cr 0.035 Nb 0.5 P 2 O 7 。
The luminescent powder can be effectively excited by blue light and red light within the range of 350-750 nm, and the main excitation peak is positioned at 465nm. The emission spectrum covers 650-1200 nm, and the main emission peak is at 850nm. The relative luminous intensity reached 75% under excitation with 460nm blue light (see table 1).
Example 5
According to chemical formula Ga 0.498 Cr 0.002 Nb 0.5 P 2 O 7 Weighing 0.00249mol Ga 2 O 3 、0.0001mol Cr 2 O 3 、0.0025mol Nb 2 O 5 And 0.001mol P 2 O 5 The raw materials are all analytically pure, the raw materials are fully ground for 30min, mixed uniformly, put into an alumina crucible, baked for 24h at 950 ℃, and after cooling to room temperature, the product is crushed, ground, washed and the like for post-treatment, thus obtaining the phosphate near infrared luminescent material, the chemical composition of which is Ga 0.498 Cr 0.002 Nb 0.5 P 2 O 7 。
The luminescent powder can be effectively excited by blue light and red light within the range of 400-750 nm, and the main excitation peak is located at 445nm. The emission spectrum covers 700-1250 nm, and the main emission peak is at 870nm. The relative luminous intensity reached 73% under excitation with 460nm blue light (see table 1).
Example 6
The formula of the luminescent powder prepared In the same manner as In example 5 is shown as In 0.3 Cr 0.2 Nb 0.5 P 2 O 7 The emission peak wavelength and the relative luminous intensity of the obtained phosphate near infrared luminous material are shown in table 1.
Example 7
The formula of the luminescent powder prepared in the manner of example 5 is shown as Al 0.25 Ga 0.2 Cr 0.05 Ta 0.5 P 2 O 7 The emission peak wavelength and the relative luminous intensity of the obtained phosphate near infrared luminous material are shown in table 1.
Example 8
The formula of the luminescent powder prepared In the same manner as In example 5 is shown as In 0.1 Ga 0.32 Cr 0.08 Ta 0.5 P 2 O 7 The emission peak wavelength and the relative luminous intensity of the obtained phosphate near infrared luminous material are shown in table 1.
Example 9
The formula of the luminescent powder prepared in the same manner as in example 5 is represented by Sc 0.22 Ga 0.22 Cr 0.06 Ta 0.5 P 2 O 7 The emission peak wavelength and the relative luminous intensity of the obtained phosphate near infrared luminous material are shown in table 1.
Example 10
According to example 5The chemical formula of the luminescent powder prepared by the method is expressed as Al 0.15 In 0.27 Cr 0.07 Ta 0.25 Nb 0.25 P 2 O 7 The emission peak wavelength and the relative luminous intensity of the obtained phosphate near infrared luminous material are shown in table 1.
Example 11
The formula of the luminescent powder prepared in the manner of example 5 is shown as Al 0.05 Ga 0.37 Cr 0.08 Ta 0.4 Nb 0.1 P 2 O 7 The emission peak wavelength and the relative luminous intensity of the obtained phosphate near infrared luminous material are shown in table 1.
Example 12
The formula of the luminescent powder prepared in the manner of example 5 is shown as Al 0.25 In 0.1 Cr 0.15 Ta 0.1 Nb 0.4 P 2 O 7 The emission peak wavelength and the relative luminous intensity of the obtained phosphate near infrared luminous material are shown in table 1.
TABLE 1 emission peak positions and relative luminous intensities of the phosphate near-infrared luminescent materials of examples 1 to 12 under excitation of 460nm
Table 1 shows the emission peak positions and the relative luminous intensities of the near infrared luminescent materials of examples 1 to 12 under 460nm excitation. As can be seen from Table 1, the phosphate near infrared luminescent material can be efficiently excited by blue light, and the emission peak wavelength is adjustable between 845 and 900nm, so that the requirements of the application fields of near infrared spectrum analysis technology, night vision, biological imaging and the like can be met.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. A phosphate near infrared luminescent material is characterized in that the chemical formula of the material is M 1 0.5-x Cr x M 2 0.5 P 2 O 7 ；M 1 At least one selected from Al, ga, in or Sc, M 2 Selected from Ta and/or Nb, x is more than or equal to 0.001 and less than or equal to 0.2.
2. The phosphate near infrared light emitting material of claim 1, wherein the material has a chemical formula of M 1 0.5-x Cr x Ta 0.5 P 2 O 7 Or M 1 0.5-x Cr x (Ta,Nb) 0.5 P 2 O 7 Wherein Ta is Nb is more than or equal to 1.
3. The method for preparing the phosphate near infrared luminescent material according to claim 1 or 2, comprising the following specific steps:
s1, M is 1 Compounds, M 2 Grinding and mixing the compound, the P compound and the Cr compound uniformly to obtain a mixture;
s2, sintering the mixture in the air at 900-1100 ℃, and crushing and grinding the product to obtain the phosphate near infrared luminescent material.
4. A method for preparing a phosphate near infrared light emitting material according to claim 3, wherein M is as defined in step S1 1 The compound is more than one of aluminum oxide, aluminum hydroxide, aluminum nitrate, gallium oxide, indium oxide, scandium oxide or scandium nitrate; the M is 2 The compound is more than one of tantalum oxide, tantalum hydroxide, niobium oxide or niobium hydroxide; the P compound is more than one of ammonium hydrogen phosphate, ammonium dihydrogen phosphate or phosphorus pentoxide; the Cr compound is chromium oxide and/or chromium nitrate.
5. The method for preparing a phosphate near infrared light emitting material according to claim 3, wherein the sintering time in step S2 is 4 to 48 hours.
6. Use of the phosphate near infrared luminescent material according to claim 1 or 2 in a light conversion device.
7. The use of claim 6, wherein the light conversion device is a near infrared LED device.
Priority Applications (1)
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