CN116376551B - Near-infrared fluorescent powder, preparation method thereof and near-infrared light-emitting device - Google Patents
Near-infrared fluorescent powder, preparation method thereof and near-infrared light-emitting device Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title description 6
- 239000000126 substance Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000000295 emission spectrum Methods 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 19
- 230000005284 excitation Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 6
- -1 ammonium halides Chemical class 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 150000008045 alkali metal halides Chemical class 0.000 claims description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims 1
- 239000011651 chromium Substances 0.000 description 26
- 239000011575 calcium Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 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 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 2
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 239000012856 weighed raw material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 1
- 229910001633 beryllium fluoride Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
-
- 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
- C09K11/7706—Aluminates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The application belongs to the technical field of luminescent materials, and discloses near infrared fluorescent powder, wherein the chemical general formula of the near infrared fluorescent powder is A a M b N c O 19 xD; the A is one or two of Mg, ca, sr, ba elements; m is at least two of Ga, al, B, in elements; the N is trivalent Sc element; the D is Cr 2+ Ions or Cr 3+ The ion, near infrared fluorescent powder with the chemical general formula can be excited by wavelengths of 250nm-280nm, 360nm-460nm and 540nm-600nm and generate an emission spectrum with the wavelength range of 700nm-850nm, which represents that the ion can be excited by purple light, blue light and visible light to generate high-efficiency near infrared light.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to near infrared fluorescent powder, a preparation method thereof and a near infrared luminescent device.
Background
In recent years, the application of near infrared light in the fields of plant illumination, food, medical detection, biological identification, remote sensing control and the like is rapidly developed, and near infrared LEDs have attracted wide attention from researchers at home and abroad due to a series of advantages of small size, low power consumption, good directivity and the like.
The near infrared LED can be realized by a near infrared semiconductor chip, but the technology has the problems of high cost, immature technology and the like. In contrast, the near infrared LED of the semiconductor blue light chip composite near infrared luminescent material becomes an international research hot spot due to the characteristics of simple packaging technology, low cost, high luminous efficiency and the like. Therefore, new near infrared luminescent materials for near infrared LEDs with different wavebands are urgently needed to be discovered to realize diversified application requirements.
Chinese patent 20201182949. X discloses a broadband near infrared luminescent material, a method for preparing the same and a luminescent device, a broadband near infrared luminescent material having a chemical composition of a 3 B 3 M 2 F 12 ：xCr 3+ Representation, wherein: the element A and the element B are different alkali metals; the M element is a trivalent metal element; cr (Cr) 3+ Is luminescence center ion, x is more than or equal to 0.01at.% and less than or equal to 50at.%. Preferably, the a element is selected from one of Li, na, K, rb, cs; preferably, the metal is one of Li, na and K, and more preferably Na. Preferably, the B element is selected from one of Li, na, K, rb, cs, which is different from the a element; preferably one of Li, na and K; more preferably Li. Preferably, the M element is selected from at least one of transition metals and rare earth elements; for example, the M element is selected from at least one of Al, ga, in, fe, sc, ti. Preferably, the M element is Al, ga, in, fe, sc or Ti.
The luminescent material prepared by the scheme has the advantages that the luminescent material can be excited by visible light (purple light, blue light, yellow light or red light) to generate a wide near infrared emission spectrum, and the problems of weak luminous intensity, poor luminous thermal stability and narrow half-peak width of the emission spectrum of a single-component luminescent material in the prior art are solved.
Chinese patent 202211079797.X discloses a trivalent chromium ion activated broadband near infrared luminescent material and its preparation method, the luminescent material uses alkali metal aluminate oxide as matrix, trivalent chromium ion as activator, its chemical formula is expressed as K 2.3 Na 0.7 Al 0.9-x Ga 0.1 O 3 xCr, wherein x is the mole number of chromium ions replacing aluminum ions, and x is more than or equal to 0.0045 and less than or equal to 0.09. The broadband near infrared luminescent material provided by the invention can be effectively excited by near ultraviolet blue light wave band to emit 700-1100 nm broadband near infrared light, has lower phonon energy and excellent physicochemical stability, and compared with fluoride-based fluorescent powder, the fluorescent powder can be in moist stateApplication in the environment.
Through research, the near infrared fluorescent powder with the luminous wave band of 700nm-850nm can be obtained by further optimizing related elements, and the composition of the near infrared fluorescent powder is Ca 0.85 Ga 4 Al 7.4 Sc 0.5 Cr 0.25 O 19 The near infrared fluorescent powder can be excited by ultraviolet light, blue light and visible light, so that the technical problems of narrow emission spectrum range, low luminous intensity and the like of the near infrared fluorescent powder in the prior art are solved, and the gap of the high-intensity wide-spectrum near infrared fluorescent powder with the emission peak wavelength of 780nm is filled. The near infrared fluorescent powder can be used for preparing an LED light-emitting device, the emission peak wavelength range of the light-emitting device under excitation of a blue light chip is 700-850nm, the defects of other near infrared light acquisition modes can be avoided, and the near infrared fluorescent powder can be widely applied to various traditional or novel fields such as full-spectrum healthy illumination, plant illumination, ultra-high color gamut liquid crystal display backlight, calibration light sources and security monitoring fields.
In the subsequent studies, it was found that the luminous intensity thereof was yet to be improved.
The problem that this scheme needs to solve: how to develop a near infrared fluorescent powder which can stably emit fluorescent powder with the wavelength of 700-850nm and has excellent luminous intensity.
Disclosure of Invention
The invention aims to provide near infrared fluorescent powder which can be excited by purple light, blue light and visible light to generate high-efficiency near infrared light, and the excited near infrared light has the advantage of high luminous intensity.
Meanwhile, the application also discloses a preparation method of the near infrared fluorescent powder and a near infrared light-emitting device.
In order to achieve the above purpose, the technical scheme adopted in the application is as follows:
a near infrared fluorescent powder has a chemical formula of A a M b N c O 19 :xD；
The A is one or two of Mg, ca, sr, ba elements;
m is at least two of Ga, al, B, in elements;
the N is trivalent Sc element;
the D is Cr 2+ Ions or Cr 3+ Ions;
the a, b and c satisfy the following conditions: a is more than or equal to 0.5 and less than or equal to 1.2, b is more than or equal to 10 and less than or equal to 12, c is more than or equal to 0.1 and less than or equal to 1, and x is more than or equal to 0.05 and less than or equal to 0.6;
the A is Ca element, and the M comprises Ga element and Al element.
Preferably, the excitation wavelength range of the near infrared fluorescent powder is 250nm-280nm, 360nm-460nm and 540nm-600nm;
the wavelength range of the emission spectrum of the near infrared fluorescent powder is 700nm-850nm.
In addition, the patent discloses a preparation method of the near infrared fluorescent powder, which is used for the near infrared fluorescent powder and comprises the following steps:
step 1: mixing the raw materials A, M, N and D with a fluxing agent accounting for 0.3% -1% of the total mass of the raw materials to obtain a mixed material;
step 2: placing the mixed material prepared in the step 1 in a reducing atmosphere for one-time sintering to obtain a presintering product;
step 3: placing the presintering product obtained in the step 2 in a reducing atmosphere for secondary sintering to obtain a sintering product;
step 4: crushing, sieving and washing the sintered product to obtain near infrared fluorescent powder;
the raw material A is one or two selected from Mg, ca, sr, ba compounds;
the raw material M is at least two compounds selected from Ga, al, B, in;
the N is trivalent Sc metal element;
the raw material D is a Cr compound;
obtaining the compound with the chemical general formula A a M b N c O 19 xD near infrared fluorescent powder;
the a, b, c, x satisfies the following conditions: a is more than or equal to 0.5 and less than or equal to 1.2, b is more than or equal to 10 and less than or equal to 12, c is more than or equal to 0.1 and less than or equal to 1, and x is more than or equal to 0.05 and less than or equal to 0.6.
Preferably, the primary sintering temperature is 1100-1200 ℃ and the time is 2-4 hours;
the secondary sintering temperature is 1300-1500 ℃ and the time is 4-8 hours;
the temperature rising rate of the primary sintering and the secondary sintering is 1-5 ℃/min;
it should be noted that: the primary sintering and the secondary sintering are preferably heated along with the furnace;
the primary sintering is to promote the decomposition of calcium carbonate and the primary reaction of other materials to obtain presintered products, and then the presintered products are crushed and sieved to disperse the agglomerated materials in the presintered process, so that the uniformity of the mixed materials is improved, and the crystallization of the sample in the secondary sintering is facilitated. If the temperature is too low or too short, the decomposition of calcium carbonate may be incomplete, whereas if the temperature is too high and the time is too long, the reactivity of the raw materials may be affected. The secondary sintering is to bond particles generated by heating raw materials, and then diffuse and crystallize the raw materials through substance migration, so that the fluorescent powder is obtained, and the sintering temperature and time influence the crystallization effect, thereby influencing the crystallization degree, concentration and granularity of the fluorescent powder.
The reducing atmosphere is hydrogen atmosphere or carbon monoxide atmosphere. It is contemplated that methane, ammonia, sulfur monoxide may also be suitable for use in the present invention.
Preferably, the cosolvent is selected from at least one of boric acid, alkali metal halides, alkaline earth metal fluorides, ammonium halides.
More preferably, the cosolvent includes, but is not limited to, at least one of boric acid, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, rubidium fluoride, rubidium chloride, rubidium bromide, rubidium iodide, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, ammonium chloride, ammonium bromide, ammonium iodide.
Preferably, the a, b, c, x satisfies the following condition: a is more than or equal to 0.7 and less than or equal to 1; b is more than or equal to 10.7 and less than or equal to 11.7; c is more than or equal to 0.2 and less than or equal to 1; x is more than or equal to 0.1 and less than or equal to 0.5;
more preferably, a values include, but are not limited to, 0.7, 0.8, 0.9, 1.0;
b values include, but are not limited to, 10.7, 10.8, 10.9, 11.0, 11.1, 11.3, 11.5, 11.6, 11.7;
c values include, but are not limited to, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0;
values of x include, but are not limited to, 0.1, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50.
In addition, a near infrared light emitting device, the near infrared fluorescent powder and an excitation source are also disclosed.
Preferably, the wavelength range of the excitation source is within the excitation wavelength range of the near infrared phosphor.
More preferably, the wavelength range of the excitation source includes, but is not limited to, at least one of 250nm-280nm, 360nm-460nm, 540nm-600 nm.
The beneficial effects of this application are:
the near infrared fluorescent powder with the light-emitting wave band being between 700 and 850nm can be excited by purple light, blue light and visible light, and fills the gap of the high-intensity wide-spectrum near infrared fluorescent powder with the emission peak wavelength being 780nm, and the fluorescent powder keeps excellent light-emitting intensity.
Drawings
FIG. 1 is a fluorescence spectrometer spectrum of example 1;
FIG. 2 is a fluorescence spectrometer spectrum of comparative example 1.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which specific conditions, either conventional or manufacturer-suggested, are not explicitly stated. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The near infrared phosphor of this embodiment has a chemical formula of Ca 0.85 Ga 4 Al 7.4 Sc 0.5 Cr 0.25 O 19 The method comprises the steps of carrying out a first treatment on the surface of the Weighing 9.6g of raw material calcium carbonate, 42.4g of gallium oxide, 42.6g of aluminum oxide and the following components according to the stoichiometric ratio3.9g of scandium, 2.1g of chromium oxide and 0.6g of boric acid auxiliary agent, transferring the weighed raw materials into a ball milling tank, adding agate balls, and mixing for 4 hours by using a roller type ball mill;
filling the mixed powder into a 250mL alumina crucible, reversely buckling a 750mL alumina crucible, and filling carbon powder on a base for placing the 250mL crucible; and (3) carrying out primary sintering by using a muffle furnace, firstly heating the muffle furnace to 1150 ℃ at a heating rate of 3 ℃/min, calcining for 4 hours, cooling to room temperature along with the furnace to obtain a presintered product, crushing and sieving the presintered product, heating to 1400 ℃ at a heating rate of 3 ℃/min, carrying out secondary sintering for 4 hours, cooling to room temperature along with the furnace to obtain a sintered product, and finally crushing, sieving and washing the sintered product to obtain the near infrared fluorescent powder.
Example 2
The near infrared phosphor of this embodiment has a chemical formula of Ca 0.85 Ga 4 Al 7.25 Sc 0.65 Cr 0.25 O 19 The method comprises the steps of carrying out a first treatment on the surface of the Weighing 9.6g of raw materials of calcium carbonate, 42.3g of gallium oxide, 41.8g of aluminum oxide, 5.1g of scandium oxide, 2.3g of chromium oxide and 0.6g of sodium chloride auxiliary agent according to a stoichiometric ratio, transferring the weighed raw materials into a ball milling tank, adding agate balls, and mixing materials for 4 hours by using a roller ball mill;
placing the uniformly mixed powder into a 250mL alumina crucible, sintering the powder once by using a tube furnace, introducing nitrogen mixed with 5% hydrogen, heating the tube furnace to 1150 ℃ at a heating rate of 4 ℃/min, calcining for 4 hours, cooling the tube furnace to room temperature to obtain a presintered product, crushing and sieving the presintered product, sintering the presintered product for 4 hours at 1400 ℃ for cooling the presintered product to room temperature, obtaining a sintered product, and finally carrying out post-treatment such as crushing, sieving, washing and the like on the sintered product to obtain the near infrared fluorescent powder.
Example 3
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.7 Ga 3.7 Al 7.6 Sc 0.5 Cr 0.5 O 19 。
Example 4
Basic phase with example 1The difference is that the chemical formula of the near infrared fluorescent powder is Ca 0.7 Ga 3.8 Al 7.6 Sc 0.5 Cr 0.4 O 19 。
Example 5
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.8 Ga 3.4 Al 8.3 Sc 0.2 Cr 0.3 O 19 。
Example 6
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.85 Ga 5 Al 6.15 Sc 0.8 Cr 0.2 O 19 。
Example 7
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 1.0 Ga 4 Al 6.9 Sc 1.0 Cr 0.1 O 19 。
Example 8
Substantially the same as in example 1, except that the primary sintering temperature was 1100℃for 4 hours, and the secondary sintering temperature was 1500℃for 4 hours.
Example 9
Substantially the same as in example 1, except that the temperature of the primary sintering was 1200℃for 2 hours, the temperature of the secondary sintering was 1300℃for 8 hours.
Example 10
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Mg 0.85 In 4 B 7.4 Sc 0.5 Cr 0.25 O 19 。
Example 11
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ba 0.85 Ga 4 B 7.4 Sc 0.5 Cr 0.25 O 19 。
Example 12
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Sr 0.85 Al 4 In 7.4 Sc 0.5 Cr 0.25 O 19 。
Example 13
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.4 Mg 0.45 Ga 4 Al 7.4 Sc 0.8 5 Cr 0.25 O 19 。
Example 14
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.4 Mg 0.45 Ga 3 B 1.3 Al 4.4 In 2 Sc 0.85 Cr 0.25 O 19 。
Comparative example 1
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.85 Ga 4 Al 7.9 Cr 0.25 O 19 。
Comparative example 2
Substantially the same as in example 1, except that the near infrared phosphor has the chemical formula Ca 0.85 Al 11.4 Sc 0.5 Cr 0.25 O 19 。
Comparative example 3
Substantially the same as in example 1, except that the near infrared phosphor has the chemical formula Ca 0.85 Ga 11.4 Sc 0.5 Cr 0.25 O 19 。
Comparative example 4
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.85 Ga 4 Al 7.85 Sc 0.05 Cr 0.25 O 19 。
Comparative example 5
Substantially the same as in example 1, except that the near infrared phosphor has a chemical formula of Ca 0.85 Ga 3.1 Al 7.4 Sc 1.5 Cr 0.25 O 19 。
Comparative example 6
Substantially the same as in example 1, except that near infrared fluorescence was usedThe chemical formula of the light powder is Na 0.3 Ca 0.7 Ga 4 Al 7.4 Sc 0.5 Cr 0.25 O 19 。
Performance testing
The samples of the examples and comparative examples were tested for emission peak, half-width and relative brightness in Ca 0.85 Ga 4 Al 7.4 Sc 0.5 Cr 0.25 O 19 The light-emitting luminance of the other examples and comparative examples was measured based on the light-emitting luminance of 100.
Table 1: peak wavelength and half-peak width of near infrared fluorescent powder under 450nm wavelength excitation
Analysis of results:
1. as can be seen from a comparison of example 1 and comparative example 1, the spectral widths of both are similar in the presence of A, M and M being Ga, al; however, the brightness of example 1 is higher than that of comparative example 1 because: the addition of scandium element is helpful for improving the luminous brightness;
2. as can be seen from comparison of example 1 with comparative example 2 and comparative example 3, M must be present for 2 elements simultaneously to obtain an emission spectrum having a peak wavelength of around 780nm and a broad half-width, which may be due to: the absence of one of the elements may cause severe deformation of the crystal structure, thus altering the crystal field;
and it can be found from comparative examples 2 and 3 that the simultaneous presence of Al and Sc is very necessary for the light emission luminance; the simultaneous presence of Al and Ga is important for half-peak width.
3. It can be seen from examples 1 and 4 and 5 that when the amount of trivalent scandium is too small or too large, the relative brightness is also affected, probably because: the content of scandium has an influence on crystallization, thereby influencing brightness;
4. as can be seen from examples 1 and 6, when the portion of A is sodium, the luminance is poor, that is, the selection of A element in the present invention should be careful to avoid contamination of the raw material as much as possible.
5. Example 3 for achieving the purpose of improving both from the half-width and the luminance simultaneously
(Ca 0.7 Ga 3.7 Al 7.6 Sc 0.5 Cr 0.5 O 19 ) And 13 (Ca) 0.4 Mg 0.45 Ga 4 Al 7.4 Sc 0.85 Cr 0.25 O 19 ) It should be noted that modifications within the scope of the present invention do not preclude the presence of more or equally superior products.
The components not listed in the examples of the present invention are considered to be within the scope of the present invention as long as they achieve similar or slightly superior results within the scope of the claims of the present invention.
Claims (9)
1. A near infrared fluorescent powder is characterized in that the chemical general formula of the near infrared fluorescent powder is A a M b N c O 19 :xD；
The A is one or two of Mg, ca, sr, ba elements;
m is at least two of Ga, al, B, in elements;
the N is trivalent Sc element;
the D is Cr 3+ Ions;
the a, b, c, x satisfies the following conditions: a is more than or equal to 0.5 and less than or equal to 1.2, b is more than or equal to 10 and less than or equal to 12, c is more than or equal to 0.1 and less than or equal to 1, and x is more than or equal to 0.05 and less than or equal to 0.6.
2. The near infrared phosphor of claim 1, wherein a comprises Ca element and M is Ga element and Al element.
3. The near infrared phosphor of claim 1, wherein the near infrared phosphor has an excitation wavelength in the range of 250nm to 280nm, 360nm to 460nm, 540nm to 600nm;
the wavelength range of the emission spectrum of the near infrared fluorescent powder is 700nm-850nm.
4. A method for preparing the near infrared phosphor according to any one of claims 1 to 3, comprising the steps of:
step 1: mixing a raw material A1, a raw material M1, a raw material N1, a raw material D1 and a fluxing agent accounting for 0.3% -1% of the total mass of the raw materials to prepare a mixed material;
step 2: placing the mixed material prepared in the step 1 in a reducing atmosphere for one-time sintering to obtain a presintering product;
step 3: placing the presintering product obtained in the step 2 in a reducing atmosphere for secondary sintering to obtain a sintering product;
step 4: crushing, sieving and washing the sintered product to obtain near infrared fluorescent powder;
the raw material A1 is one or two selected from Mg, ca, sr, ba compounds;
the raw material M1 is at least two compounds selected from Ga, al, B, in;
the N1 is trivalent Sc metal element;
the raw material D1 is a Cr compound;
obtaining the compound with the chemical general formula A a M b N c O 19 xD near infrared fluorescent powder;
the A is one or two of Mg, ca, sr, ba elements;
m is at least two of Ga, al, B, in elements;
the N is trivalent Sc element;
the D is Cr 3+ Ions;
the a, b, c, x satisfies the following conditions: a is more than or equal to 0.5 and less than or equal to 1.2, b is more than or equal to 10 and less than or equal to 12, c is more than or equal to 0.1 and less than or equal to 1, and x is more than or equal to 0.05 and less than or equal to 0.6.
5. The method for preparing near infrared fluorescent powder according to claim 4, wherein the primary sintering temperature is 1100-1200 ℃ for 2-4 hours;
the secondary sintering temperature is 1300-1500 ℃ and the time is 4-8 hours;
the primary sintering and the secondary sintering are heated along with a furnace in the sintering process, and the heating rate is 1-5 ℃/min;
the reducing atmosphere is hydrogen atmosphere or carbon monoxide atmosphere.
6. The method of producing near infrared phosphor according to claim 4, wherein the flux is at least one selected from boric acid, alkali metal halides, alkaline earth metal fluorides, ammonium halides.
7. The method of claim 4, wherein a, b, c, x satisfies the following conditions: a is more than or equal to 0.7 and less than or equal to 1; b is more than or equal to 10.7 and less than or equal to 11.7; c is more than or equal to 0.2 and less than or equal to 1; x is more than or equal to 0.1 and less than or equal to 0.5.
8. A near infrared light emitting device comprising the near infrared phosphor of any one of claims 1 to 3 and an excitation source.
9. The near infrared light emitting device of claim 8, wherein the excitation source has a wavelength range within an excitation wavelength range of the near infrared phosphor.
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| Chromium Ion Pair Luminescence: A Strategy in Broadband Near-Infrared Light-Emitting Diode Design;Veeramani Rajendran等;J. Am. Chem. Soc;第143卷;第19058−19066页 * |
| Design and tuning Cr3+-doped near-infrared phosphors for multifunctional applications via crystal field engineering;Shuaishuai Yu等;Dalton Trans;第51卷;第2313–2322页 * |
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