CN113773837A - Near-infrared luminescent material, preparation method thereof and luminescent device containing material - Google Patents
Near-infrared luminescent material, preparation method thereof and luminescent device containing material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 183
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000004020 luminiscence type Methods 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- -1 oxide Chemical compound 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 24
- 238000001228 spectrum Methods 0.000 abstract description 13
- 238000005090 crystal field Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 description 124
- 238000001816 cooling Methods 0.000 description 84
- 239000002994 raw material Substances 0.000 description 81
- 239000011777 magnesium Substances 0.000 description 80
- 239000010936 titanium Substances 0.000 description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 66
- 229910052808 lithium carbonate Inorganic materials 0.000 description 47
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 46
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 45
- 239000000395 magnesium oxide Substances 0.000 description 44
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 43
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 41
- 229910000423 chromium oxide Inorganic materials 0.000 description 41
- 229910052593 corundum Inorganic materials 0.000 description 40
- 239000010431 corundum Substances 0.000 description 40
- 239000004570 mortar (masonry) Substances 0.000 description 38
- 239000004408 titanium dioxide Substances 0.000 description 33
- 239000011701 zinc Substances 0.000 description 15
- 238000000295 emission spectrum Methods 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000004907 flux Effects 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000001748 luminescence spectrum Methods 0.000 description 3
- 238000004497 NIR spectroscopy Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000009700 powder processing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004424 eye movement Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/681—Chalcogenides
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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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/681—Chalcogenides
- C09K11/682—Chalcogenides with zinc or cadmium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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- H01L33/502—Wavelength conversion materials
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Abstract
The application provides a near-infrared luminescent material, a preparation method thereof and application thereof in a strain sensor, wherein the general formula of the luminescent material is as follows: li2+x‑yNayA3M1‑zO6:zCr3+(ii) a X is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.5, and z is more than 0 and less than 1.0; a is one or two of Mg and Zn; m is one or more of Ti, Zr, Hf, Ge, Si and Sn; mainly takes broadband near-infrared luminescence as main material. The invention mainly uses Li2O·MgO·MO2As a base component, Li is a regulatory matrix component; cr is a luminescent ion and participates in the regulation and control of a crystal field; the Cr content can regulate and control the crystal field of the matrix component, influence the near-infrared light emission center and half-peak width, and obtain the broadband near-infrared light-emitting luminescent material with different light emission peak positions and spectrum peak shapes. The luminescent material can be blueThe light excitation and the blue light chip form a high-efficiency near infrared light emitting device which can be used in various fields of near infrared LEDs.
Description
Technical Field
The application relates to the technical field of luminescent materials, in particular to a near-infrared luminescent material, a preparation method thereof and a near-infrared luminescent device containing the material.
Background
In recent years, with diversification of near-infrared light applications and a rapidly expanding demand of the near-infrared market, more and more attention is focused on the near-infrared field. According to ASTM definition, near infrared light is electromagnetic wave with wavelength in 780-2526 nm range, and conventionally divides the near infrared region into two regions of near infrared short wave (780-1100 nm) and near infrared long wave (1100-2526 nm). At present, near infrared light has important application in various fields such as health monitoring, iris recognition, face recognition, eye movement tracking and the like. Particularly, in the application of near infrared spectroscopy, with the miniaturization and convenience of near infrared spectroscopy, the miniaturization and convenience of the near infrared emission light source are also required. Near infrared light emitting diodes (NIR LEDs) are one of the near infrared light sources, and have the characteristics of convenience and small size, and enter more lines of sight of people.
At present, the market of near-infrared LEDs is mature near-infrared chips; broadband near-infrared light sources are formed by combining near-infrared chips with different emission centers, and therefore the broadband near-infrared light sources cannot be well matched with miniaturized near-infrared spectrum applications. The fluorescent powder covered near infrared LED (NIRpc-LED) can combine fluorescent powder with broadband near infrared light emission by utilizing a mature purple light chip or a blue light chip, so that the broadband near infrared LED with excellent performance and high radiant flux is obtained. At present, there are reports (Super broadside near-isolated Phosphors with High radial Flux as Future Light Sources for Spectroscopy applications. ACS Energy Letters 2018,3, (11),2679-3+La doping3Ga5GeO14Obtaining the ultra-wideband near-infrared luminescent material La3Ga5GeO14:Cr3+The near-infrared emission of the ultra-wideband is realized under the excitation of blue light, and the packaged near-infrared LED is at 350mA has a radiant flux of 18.2mW under the test conditions.
It is expected that the broadband near-infrared luminescent phosphor with excellent performance and high efficiency is still in need of development.
Disclosure of Invention
In view of the above, the present application provides a near-infrared luminescent material, a preparation method thereof, and a near-infrared luminescent device containing the material, the near-infrared luminescent material provided by the present invention can be excited by blue light to emit near-infrared light, a series of near-infrared luminescent materials with different emission peak positions, spectrum peak shapes, and half-peak widths can be obtained by regulation, and the materials mainly give priority to broadband near-infrared luminescence, have excellent luminescent properties, and can form a high-efficiency near-infrared LED with blue light.
The invention provides a near-infrared luminescent material, which has a general formula shown in formula 1:
Li2+x-yNayA3M1-zO6:zCr3+formula 1;
wherein x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.5, and z is more than 0 and less than 1.0;
a is selected from one or two of Mg and Zn;
m is selected from one or more of elements Ti, Zr, Hf, Ge, Si and Sn;
the near-infrared luminescent material mainly takes broadband near-infrared luminescence.
The invention provides a broadband near-infrared luminescent material with an adjustable luminescence spectrum peak position, which can be effectively excited by blue light, has excellent luminescence property and is beneficial to application in luminescent devices.
For the atomic ratio of the elements in formula 1, it is preferable that x is 0. ltoreq. x.ltoreq.0.8, y is 0. ltoreq. y.ltoreq.0.4, and z is 0 < z.ltoreq.0.5; preferably 0 < z.ltoreq.0.4, more preferably 0 < z.ltoreq.0.3, and the lower limit of z may be 0.0001, 0.001, or 0.01.
More preferably, x is 0. ltoreq. x.ltoreq.0.6, y is 0. ltoreq. y.ltoreq.0.2, and z is 0 < z.ltoreq.0.3. Further preferably, x is 0 or x is 0.3; y is 0.
In formula 1 of the present invention, the element a is one or two of magnesium (Mg) and zinc (Zn), preferably the element Mg; when the alloy is Mg and Zn, the content of Mg element is more than that of Zn element. The M element is one or more selected from titanium (Ti), zirconium (Zr), hafnium (Hf), germanium (Ge), silicon (Si) and tin (Sn), and is usually a single element such as Ti, Zr, Ge, Si and Sn.
In a preferred embodiment of the present invention, the near-infrared luminescent material is selected from one or more of the following structural materials (in the following molecular formula, Cr is 3+ but not shown in the expression):
Li2Mg3Ti0.98O6:0.02Cr、Li2Mg3Ti0.97O6:0.03Cr、Li2Mg3Ti0.96O6:0.04Cr、Li2Mg3Ti0.95O6:0.05Cr、Li2Mg3Ti0.94O6:0.06Cr、Li2Mg3Ti0.93O6:0.07Cr、Li2Mg3Ti0.92O6:0.08Cr、Li2Mg3Ti0.91O6:0.09Cr、Li2Mg3Ti0.9O6:0.1Cr、Li2Mg3Ti0.85O6:0.15Cr、Li2.3Mg3Ti0.98O6:0.02Cr、Li2Mg3Zr0.98O6:0.02Cr、Li2Mg3Hf0.98O6:0.02Cr、Li2Mg3Sn0.98O6:0.02Cr、Li2.3Mg3Ti0.93Hf0.05O6:0.02Cr、Li2.3Mg3Ti0.93Si0.05O6:0.02Cr、Li2.3Mg3Ti0.93Ge0.05O6:0.02Cr、Li2Zn3Ti0.98O6:0.02Cr、Li2Zn3Sn0.98O6:0.02Cr。
the luminescent material of the invention mainly takes broadband near-infrared luminescence as main material; specifically, the near-infrared luminescent material emits near-infrared light of 650-1400nm, and the central peak position of the near-infrared luminescence is adjustable.
Preferably, in formula 1, the content z of chromium (Cr) element can regulate the central peak position of near-infrared luminescence; z can regulate the half-peak width and the spectral peak shape of near-infrared luminescence.
In one embodiment of the present invention, a is Mg element, M is Ti element, x is 0, y is 0, z is 0.02, and the composition of the light emitting material is Li2Mg3Ti0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg, M is Ti, x is 0, y is 0, z is 0.05, and the composition of the light emitting material is Li2Mg3Ti0.95O6:0.05Cr；
In another embodiment of the present invention, a is Mg, M is Ti, x is 0, y is 0, z is 0.07, and the composition of the light emitting material is Li2Mg3Ti0.93O6:0.07Cr；
In another embodiment of the present invention, a is Mg, M is Ti, x is 0, y is 0, z is 0.10, and the composition of the light emitting material is Li2Mg3Ti0.9O6:0.1Cr；
In another embodiment of the present invention, a is Mg, M is Ti, x is 0, y is 0, z is 0.15, and the composition of the light emitting material is Li2Mg3Ti0.85O6:0.15Cr；
In another embodiment of the present invention, a is Mg, M is Sn, x is 0, y is 0, z is 0.02, and the composition of the light emitting material is Li2Mg3Sn0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg, M is Zr, x is 0, y is 0, and z is 0.02, and the composition of the light emitting material is Li2Mg3Zr0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg element, M is Hf element, x is 0, y is 0, z is 0.02, and the composition of the light emitting material is Li2Mg3Hf0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg element, M is Ti element, x is 0.3, y is 0, and z is 0.02, and the light emission is performedThe composition of the material is Li2.3Mg3Ti0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg, M is Sn, x is 0.3, y is 0, z is 0.02, and the composition of the light emitting material is Li2.3Mg3Sn0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg, M is Zr, x is 0.3, y is 0, and z is 0.02, and the composition of the light emitting material is Li2.3Mg3Zr0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg element, M is Hf element, x is 0.3, y is 0, z is 0.02, and the composition of the light emitting material is Li2.3Mg3Hf0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg, M is Ti, x is 0, y is 0.1, z is 0.02, and the composition of the light emitting material is Li2Na0.1Mg3Ti0.98O6:0.02Cr；
In another embodiment of the present invention, a is Mg or Zn, M is Ti, x is 0, y is 0, z is 0.02, and the composition of the light emitting material is Li2Mg2.9Zn0.1Ti0.98O6:0.02Cr；
In another embodiment of the present invention, a is Zn element, M is Ti element, x is 0, y is 0, z is 0.02, and the composition of the light emitting material is Li2Zn3Ti0.98O6:0.02Cr；
In another embodiment of the present invention, a is Zn element, M is Sn element, x is 0, y is 0, z is 0.02, and the composition of the light emitting material is Li2Zn3Sn0.98O6:0.02Cr。
The near-infrared luminescent material provided by the embodiment of the invention has a structure shown in a formula 1, and is formed by Li2O·MgO·MO2As a basic component, Li element is used as a regulation matrix component; cr is a luminescent ion and participates in the regulation and control of a crystal field; the content of Cr element can effectively regulate and control the crystal field of matrix component, and influence on the fieldThe infrared light emission center and the half peak width obtain a series of broadband near-infrared luminous luminescent materials with different luminous peak positions and spectrum peak shapes. The obtained luminescent material can be effectively excited by blue light, and forms a high-efficiency near-infrared light emitting device with the blue light chip, so that the luminescent material can be used in various fields of near-infrared LEDs.
The invention also provides a preparation method of the near-infrared luminescent material in the technical scheme, which comprises the following steps:
s1) mixing a lithium source compound, a sodium source compound, a chromium source compound, a compound containing an A element and a compound containing an M element to obtain a mixture; the sodium source compound is optionally added;
s2) sintering the mixture to obtain the near-infrared luminescent material with the structure shown in the formula 1.
In an embodiment of the present invention, the lithium source compound is a lithium element-containing compound selected from one or more of a carbonate, a nitrate, a phosphate, an oxide, a fluoride, and a chloride of lithium; in a preferred embodiment, the lithium source compound is lithium carbonate.
In an embodiment of the present invention, the sodium source compound is a compound containing sodium element, and is selected from one or more of carbonate, nitrate, phosphate, oxide, fluoride and chloride of sodium; in a preferred embodiment, the sodium source compound is sodium carbonate.
In an embodiment of the invention, the A element-containing compound is selected from one or more of A element-containing carbonate, nitrate, phosphate, oxide, fluoride; one or both of magnesium oxide and zinc oxide are preferable.
In an embodiment of the present invention, the M-containing compound is selected from one or more of nitrate, phosphate, oxide, fluoride of M-containing element; preferably titanium dioxide, zirconium dioxide, tin dioxide, hafnium dioxide.
In an embodiment of the present invention, the source compound of chromium is a compound containing chromium element, and is selected from one or more of nitrate, phosphate, oxide and chloride of chromium. In a preferred embodiment, the source compound of chromium is chromium oxide.
In the examples of the present invention, the source of each raw material is not particularly limited, and commercially available raw materials having a purity of 99% or more can be used.
In an embodiment of the present invention, the molar ratio of the lithium source compound, the sodium source compound, the a element-containing compound, the M element-containing compound, and the chromium source compound is preferably (1.5 to 3): (0-0.5): 3: (0.5-1): (0.0001 to 0.5); in the embodiment of the invention, the raw materials are mixed according to the molar ratio.
In some embodiments of the present invention, the molar ratio is specifically:
2：0：3：0.995：0.005、
2：0：3：0.99：0.01、
2：0：3：0.98：0.02、
2：0：3：0.97：0.03、
2：0：3：0.96：0.04、
2：0：3：0.95：0.05、
2：0：3：0.94：0.06、
2：0：3：0.93：0.07、
2：0：3：0.92：0.08、
2：0：3：0.91：0.09、
2：0：3：0.90：0.10、
2：0：3：0.85：0.15、
2.1：0：3：0.98：0.02、
2.2：0：3：0.98：0.02、
2.3：0：3：0.98：0.02、
2.4：0：3：0.98：0.02、
2.5: 0: 3: 0.98: 0.02 and 2: 0.1: 3: 0.98: 0.02.
in the embodiment of the present invention, the raw materials are preferably mixed by grinding, and the respective materials are sufficiently and uniformly ground to obtain a mixture. In the present invention, a fluxing agent can be added during the above grinding and mixing process, and the fluxing agent is preferably LiF or Li2CO3、MgF2(ii) a The content of the added fluxing agent is preferably 0.5-3% of the mass fraction of the mixture. Value ofIllustratively, Li2CO3As a raw material in the invention, a fluxing agent is added in some embodiments; in some embodiments of the invention, no Li addition is added2CO3The flux is not specifically described, but the positive effect of the flux on the sintering process cannot be ignored.
Sintering the obtained mixture in the embodiment of the invention; wherein, before the sintering, the method also preferably comprises pre-sintering, cooling and grinding. The pre-sintering temperature is preferably 400-1000 ℃, and the pre-sintering time is preferably 0.5-24 hours. Pre-burning and cooling; the cooling is preferably to room temperature. After cooling, the mixture was ground again to obtain a uniform powder.
Sintering the treated uniform powder in an atmosphere; the sintering atmosphere may be air, nitrogen, argon or oxygen. In the invention, the sintering temperature is preferably 1000-1500 ℃, and the sintering time is preferably 0.5-16 hours. More preferably, the sintering temperature is 1100-1500 ℃, and the sintering time is 2-10 hours. After the sintering, the invention preferably further performs grinding post-treatment, and the sample is ground into powder to obtain the luminescent material product which has the structure shown in the formula 1.
In summary, the preparation method provided in the embodiment of the present invention is to grind and mix the mixture of the raw materials of carbonate, oxide, phosphate, oxalate, nitrate, etc. of the element in the expression of formula 1, pre-bake at 400-. The material can emit 650-1400nm near infrared light under the excitation of a near ultraviolet chip or a blue light chip as a light source by controlling the types of M elements and the proportion of each element, the luminous spectrum peak position, the peak shape and the half-peak width of the material can be effectively regulated and controlled by the content of Cr element, and the material can be used as a novel near infrared luminescent material to prepare a near infrared LED light source.
According to the embodiment of the invention, the luminescent material is subjected to proper powder treatment, so that the fluorescent powder meeting the LED packaging requirements (such as uniform granularity and excellent luminous intensity) can be obtained; the powder processing mode is not particularly limited, and the powder processing mode is a conventional processing mode for preparing the packaged LED fluorescent powder in the field, and can comprise post-processing processes such as wet ball milling (crushing), particle size monitoring, passing through a mesh screen and the like. In addition, the preparation method of the embodiment of the invention is simple and convenient and is easy to operate.
The invention also provides a near-infrared LED light source, which comprises a blue light chip and a luminescent material for LED packaging; the luminescent material (phosphor) is the near-infrared luminescent material described above.
Taking the embodiment 4 of the present invention as an example, the luminescent material and the blue light chip form an NIRpc-LED, and the NIRpc-LED has the radiant flux of 31.09mW, 64.76mW and 71.56mW under the test conditions of 3V-100 mA, 3V-300 mA and 3V-420 mA, respectively.
The current near-infrared fluorescent powder has limited regulation range, and the invention realizes the peak regulation in the ultra-wide range of 720-plus 920nm through crystal field engineering. The near-infrared fluorescent powder provided by the invention can realize broadband near-infrared emission, and is widely applied to various fields such as food nondestructive rapid detection, application of near-infrared spectrum technology, plant illumination, eye tracking, iris recognition, face recognition, night vision and the like.
Drawings
To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only embodiments of the invention, and that for a person skilled in the art, other drawings can be obtained from the provided drawings without inventive effort.
FIG. 1 is a diagram showing an excitation spectrum of a near-infrared luminescent material provided in example 1 of the present invention;
FIG. 2 is a graph of the emission spectrum obtained in example 1 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system;
FIG. 3 is a graph of the emission spectrum obtained in example 1 under 460nm excitation in a fiber optic spectrometer (the detector is a CCD photodetector);
it should be noted that fig. 2 and 3 are only examples 1 and the most true description of the present invention, and are included in the scope of the present invention, although the spectrum pattern is slightly deviated due to the inconsistency of the near infrared detector;
FIG. 4 is an X-ray powder diffraction pattern of the near-infrared luminescent material provided in example 1 of the present invention;
FIG. 5 is a graph of a luminescence spectrum of a device under test conditions of 3V-100 mA and 3V-300 mA after the near-infrared luminescent material provided in example 1 is packaged with a 460nm blue light chip to prepare a near-infrared LED;
FIG. 6 is a spectrum of the emission light obtained in FLS 920-equipped near infrared detector (NIR PMT) system at 460nm excitation in example 4;
FIG. 7 is a spectrum of the emission light obtained in FLS 920-equipped near infrared detector (NIR PMT) system at 460nm excitation in example 5;
FIG. 8 is a spectrum of the emission light obtained in FLS 920-equipped near infrared detector (NIR PMT) system at 460nm excitation in example 7;
FIG. 9 is a spectrum of the emission light obtained in example 9 at 460nm excitation in FLS 920-mounted near infrared detector (NIR PMT) system;
FIG. 10 is a graph of the emission spectrum obtained in example 11 at 460nm excitation in FLS 920-mounted near infrared detector (NIR PMT) system;
FIG. 11 is a spectrum of the emission light obtained in example 12 at 460nm excitation in FLS 920-mounted near infrared detector (NIR PMT) system;
FIG. 12 is a spectrum of the emission light obtained from example 20 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system;
FIG. 13 is a spectrum of the emission light obtained in example 22 at 460nm excitation in FLS 920-equipped near infrared detector (NIR PMT) system;
FIG. 14 is a graph of the emission spectra obtained for example 24 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; these embodiments are provided so that this disclosure will be thorough and complete. The various starting materials used in the examples are, unless otherwise indicated, conventional commercial products.
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention. In the following examples, the atmosphere for sintering is mainly air.
Example 1
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material.
The obtained near-infrared luminescent material is a light green sample, and the excitation spectrum of the near-infrared luminescent material is a broadband, as shown in figure 1.
Under the excitation of blue light at 460nm, the emission center wavelength of the luminescent material is positioned near 727nm, as shown in fig. 2 and fig. 3.
Fig. 2 shows a test pattern obtained by FLS920 carrying a near infrared detector (NIR PMT).
Fig. 3 is a test pattern obtained by a fiber optic spectrometer (CCD photodetector).
It should be noted that fig. 2 and 3 are only examples 1 and the most realistic description of the present invention, although the spectrum pattern is slightly deviated due to the inconsistency of the near infrared detector, and are all included in the protection scope of the present invention.
The specific molecular formula of the obtained material is Li2Mg3Ti0.98O60.02Cr, see FIG. 4, FIG. 4 is the hairThe X-ray powder diffraction pattern of the near-infrared luminescent material provided in example 1 is shown.
The luminescent material and a 460nm blue light chip are packaged to prepare a near-infrared LED, and the emission spectrum of the device is shown in figure 5 under the test conditions of 3V-100 mA and 3V-300 mA.
FIG. 5 is a graph of a luminescence spectrum of a device under test conditions of 3V-100 mA and 3V-300 mA after the near-infrared luminescent material provided in example 1 is packaged with a 460nm blue light chip to prepare a near-infrared LED.
Example 2
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.995: 0.005, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.995O6:0.005Cr。
Example 3
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.99: 0.01, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.99O6:0.01Cr。
Example 4
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.97: 0.03, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.97O6:0.03Cr。
FIG. 6 is a graph of the emission spectra obtained in FLS 920-equipped near infrared detector (NIR PMT) system at 460nm excitation in example 4.
Example 5
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.96: 0.04, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.96O6:0.04Cr。
FIG. 7 is a graph of the emission spectra obtained in example 5 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 6
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.95: 0.05, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.95O6:0.05Cr。
Example 7
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.94: 0.06, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.94O6:0.06Cr。
FIG. 8 is a graph of the emission spectra obtained in example 7 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 8
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.93: 0.07, fully grinding and uniformly mixing the materials in a mortar, putting the materials into a corundum crucible, presintering the materials for 4 hours at 800 ℃, cooling the materials to room temperature, grinding the materials again, finally reacting the materials for 6 hours at 1280 ℃, naturally cooling the materials, taking out a sample, and carefully grinding the materials to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.93O6:0.07Cr。
Example 9
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.92: 0.08, fully grinding and uniformly mixing the materials in a mortar, putting the materials into a corundum crucible, presintering the materials for 4 hours at 800 ℃, cooling the materials to room temperature, grinding the materials again, finally reacting the materials for 6 hours at 1280 ℃, naturally cooling the materials, taking out a sample, and carefully grinding the materials to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.92O6:0.08Cr。
FIG. 9 is a graph of the emission spectra obtained in example 9 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 10
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.91: 0.09, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.91O6:0.09Cr。
Example 11
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.9: 0.1, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.9O6:0.1Cr。
FIG. 10 is a graph of the emission spectra obtained in example 11 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 12
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.85: 0.15, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.85O6:0.15Cr。
FIG. 11 is a graph of the emission spectra obtained in example 12 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 13
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.1: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.1Mg3Ti0.98O6:0.02Cr。
Example 14
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.2: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.2Mg3Ti0.98O6:0.02Cr。
Example 15
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.3: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Ti0.98O6:0.02Cr。
Example 16
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.4: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.4Mg3Ti0.98O6:0.02Cr。
Example 17
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.5: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, and finally reacting for 6 hours at 1280 DEG CAnd naturally cooling, taking out the sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.5Mg3Ti0.98O6:0.02Cr。
Example 18
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.3: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1400 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Ti0.98O6:0.02Cr。
Example 19
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), zirconium dioxide (99.99%) and chromium oxide (99.999%), and the molar ratio of the lithium carbonate to the magnesium oxide is 2: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1400 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Zr0.98O6:0.02Cr。
Example 20
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), zirconium dioxide (99.99%), chromium oxide (99.999%), and the molar ratio of the lithium carbonate to the magnesium oxide is 2.3: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1400 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Zr0.98O6:0.02Cr。
FIG. 12 is a graph of the emission spectra obtained for example 20 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 21
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), hafnium oxide (99.99%), chromium oxide (99.999%), and the molar ratio of the lithium carbonate to the magnesium oxide is 2: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1400 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Hf0.98O6:0.02Cr。
Example 22
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), hafnium oxide (99.99%), chromium oxide (99.999%), and the molar ratio of the lithium carbonate to the magnesium oxide is 2.3: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1400 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Hf0.98O6:0.02Cr。
FIG. 13 is a graph of the emission spectra obtained for example 22 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 23
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), tin dioxide (99.9%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1360 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Sn0.98O6:0.02Cr。
Example 24
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), tin dioxide (99.99%), chromium oxide (99.999%) and their mole ratioThe ratio is 2.3: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1360 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Sn0.98O6:0.02Cr。
FIG. 14 is a graph of the emission spectra obtained for example 24 at 460nm excitation in a FLS 920-mounted near infrared detector (NIR PMT) system.
Example 25
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), zirconium dioxide (99.99%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.3: 3: 0.93: 0.05: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1400 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Ti0.93Zr0.05O6:0.02Cr。
Example 26
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), hafnium dioxide (99.99%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.3: 3: 0.93: 0.05: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1400 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Ti0.93Hf0.05O6:0.02Cr。
Example 27
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), tin dioxide (99.9%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.3: 3: 0.93: 0.05: 0.02, fully grinding and mixing in a mortarAnd (3) uniformly presintering the mixture in a corundum crucible at 800 ℃ for 4 hours, cooling the mixture to room temperature, grinding the mixture again, finally reacting the mixture at 1400 ℃ for 6 hours, naturally cooling the mixture, taking out a sample, and carefully grinding the sample to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Ti0.93Sn0.05O6:0.02Cr。
Example 28
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), germanium dioxide (99.999%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.3: 3: 0.93: 0.05: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Ti0.93Ge0.05O6:0.02Cr。
Example 29
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), silicon dioxide (99.99%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2.3: 3: 0.93: 0.05: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1200 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2.3Mg3Ti0.93Si0.05O6:0.02Cr。
Example 30
The raw materials are lithium carbonate (99.99%), sodium carbonate (99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 0.1: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. Obtained byThe specific molecular formula of the material is Li2Na0.1Mg3Ti0.98O6:0.02Cr。
Example 31
The raw materials are lithium carbonate (99.99%), sodium carbonate (99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 0.3: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Na0.3Mg3Ti0.98O6:0.02Cr。
Example 32
The raw materials are lithium carbonate (99.99%), sodium carbonate (99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 0.5: 3: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Na0.5Mg3Ti0.98O6:0.02Cr。
Examples 30, 31, 32 relate to sodium and a sodium source, with Na only partially replacing Li in the general framework of Li.
Example 33
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), zinc oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 2.9: 0.1: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg2.9Zn0.1Ti0.98O6:0.02Cr。
Example 34
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), zinc oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 2.0: 1.0: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg2ZnTi0.98O6:0.02Cr。
Example 35
The raw materials are lithium carbonate (99.99%), zinc oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3.0: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Zn3Ti0.98O6:0.02Cr。
Example 36
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), zinc oxide (99.99%), tin dioxide (99.9%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 1.8: 1.2: 0.98: 0.02, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1240 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg1.8Zn1.2Sn0.98O6:0.02Cr。
Example 37
The raw materials are lithium carbonate (99.99%), zinc oxide (99.99%), tin dioxide (99.9%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3.0: 0.98: 0.02, fully grinding and mixing in a mortarAnd (3) uniformly pre-sintering the mixture in a corundum crucible at 800 ℃ for 4 hours, cooling the mixture to room temperature, grinding the mixture again, finally reacting the mixture at 1240 ℃ for 6 hours, naturally cooling the mixture, taking out a sample, and carefully grinding the sample to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Zn3Sn0.98O6:0.02Cr。
Example 38
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.8: 0.2, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.8O6:0.2Cr。
Example 39
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.7: 0.3, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.7O6:0.3Cr。
Example 40
The raw materials are lithium carbonate (99.99%), magnesium oxide (99.99%), titanium dioxide (99.8%), chromium oxide (99.999%), and the molar ratio of the raw materials is 2: 3: 0.5: 0.5, fully grinding and uniformly mixing in a mortar, putting into a corundum crucible, presintering for 4 hours at 800 ℃, cooling to room temperature, grinding again, finally reacting for 6 hours at 1280 ℃, naturally cooling, taking out a sample, and carefully grinding to obtain the near-infrared luminescent material. The specific molecular formula of the obtained material is Li2Mg3Ti0.5O6:0.5Cr。
EXAMPLE 41
According to the test method of the luminescent material in FLS920 carrying NIRPMT detector system in the embodiment 1, partial embodiment samples are detected, and the result shows that all the detected embodiment samples can be excited at 460nm and can emit near infrared light of 650-1400 nm. The luminescence peak position and half-peak width of the test examples were simultaneously tested and compared, and the results are shown in table 1.
TABLE 1 part of examples emission peak position and half-peak width
| Sample (I) | Emission center (nm) | Peak width (nm) |
| Example 1 | 727 | 87 |
| Example 3 | 723 | 71 |
| Example 4 | 735 | 121 |
| Example 5 | 742 | 132 |
| Example 6 | 754 | 158 |
| Example 7 | 762 | 174 |
| Example 8 | 776 | 188 |
| Example 9 | 789 | 197 |
| Example 10 | 797 | 200 |
| Example 11 | 804 | 201 |
| Example 12 | 831 | 205 |
| Example 20 | 775 | 176 |
| Example 22 | 791 | 181 |
| Example 24 | 777 | 188 |
| Example 38 | 875 | 227 |
| Example 39 | 890 | 236 |
| Example 40 | 916 | 258 |
As can be seen from the above examples, the near-infrared luminescent material Li provided by the invention2+x-yNayA3M1-zO6:zCr3+The material mainly takes broadband near-infrared luminescence as a main material, has excellent luminescence performance, can form an efficient near-infrared LED with blue light, and is widely applied.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A near-infrared luminescent material is characterized in that the general formula is shown as formula 1:
Li2+x-yNayA3M1-zO6:zCr3+formula 1;
wherein x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.5, and z is more than 0 and less than 1.0;
a is selected from one or two of Mg and Zn;
m is selected from one or more of elements Ti, Zr, Hf, Ge, Si and Sn;
the near-infrared luminescent material mainly takes broadband near-infrared luminescence.
2. The near-infrared luminescent material as claimed in claim 1, wherein x is 0. ltoreq. x.ltoreq.0.8, y is 0. ltoreq. y.ltoreq.0.4, and z is 0. ltoreq.z.ltoreq.0.5.
3. The near-infrared luminescent material according to claim 1, wherein a is elemental Mg; preferably, y is 0.
4. The near-infrared luminescent material according to claim 1, wherein the near-infrared luminescent material is selected from one or more of the following structural materials:
Li2Mg3Ti0.98O6:0.02Cr、Li2Mg3Ti0.97O6:0.03Cr、Li2Mg3Ti0.96O6:0.04Cr、Li2Mg3Ti0.95O6:0.05Cr、Li2Mg3Ti0.94O6:0.06Cr、Li2Mg3Ti0.93O6:0.07Cr、Li2Mg3Ti0.92O6:0.08Cr、Li2Mg3Ti0.91O6:0.09Cr、Li2Mg3Ti0.9O6:0.1Cr、Li2Mg3Ti0.85O6:0.15Cr、Li2.3Mg3Ti0.98O6:0.02Cr、Li2Mg3Zr0.98O6:0.02Cr、Li2Mg3Hf0.98O6:0.02Cr、Li2Mg3Sn0.98O6:0.02Cr、Li2.3Mg3Ti0.93Hf0.05O6:0.02Cr、Li2.3Mg3Ti0.93Si0.05O6:0.02Cr、Li2.3Mg3Ti0.93Ge0.05O6:0.02Cr、Li2Zn3Ti0.98O6:0.02Cr、Li2Zn3Sn0.98O6:0.02Cr。
5. the near-infrared luminescent material as claimed in any one of claims 1 to 4, wherein the near-infrared luminescent material emits near-infrared light of 650-1400nm, and the central peak position of the near-infrared luminescence is adjustable.
6. A method for preparing the near-infrared luminescent material of any one of claims 1 to 5, comprising the steps of:
s1) mixing a lithium source compound, a sodium source compound, a chromium source compound, a compound containing an A element and a compound containing an M element to obtain a mixture; the sodium source compound is optionally added;
s2) sintering the mixture to obtain the near-infrared luminescent material with the structure shown in the formula 1.
7. The method according to claim 6, wherein the lithium source compound is selected from one or more of a carbonate, a nitrate, a phosphate, an oxide, a fluoride, and a chloride of lithium;
the sodium source compound is selected from one or more of carbonate, nitrate, phosphate, oxide, fluoride and chloride of sodium;
the A-containing compound is selected from one or more of A-containing carbonate, nitrate, phosphate, oxide and fluoride;
the M-containing compound is selected from one or more of nitrate, phosphate, oxide and fluoride of the M-containing element;
the chromium source compound is selected from one or more of nitrate, phosphate, oxide and chloride of chromium.
8. The production method according to claim 6, wherein the molar ratio of the lithium source compound, the sodium source compound, the A element-containing compound, the M element-containing compound, and the chromium source compound is (1.5 to 3): (0-0.5): 3: (0.5-1): (0.0001 to 0.5).
9. The method according to claim 6, wherein the atmosphere for sintering is air, nitrogen, argon or oxygen; the sintering temperature is 1000-1500 ℃, and the sintering time is 0.5-16 hours.
10. The near-infrared LED light source is characterized by comprising a blue light chip and a luminescent material for LED packaging;
the luminescent material is the near-infrared luminescent material as described in any one of claims 1 to 5 or the near-infrared luminescent material prepared by the preparation method as described in any one of claims 6 to 9.
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