CN116751588A - Near infrared luminescent material, preparation method thereof and LED light source containing material - Google Patents
Near infrared luminescent material, preparation method thereof and LED light source containing material Download PDFInfo
- Publication number
- CN116751588A CN116751588A CN202310769509.1A CN202310769509A CN116751588A CN 116751588 A CN116751588 A CN 116751588A CN 202310769509 A CN202310769509 A CN 202310769509A CN 116751588 A CN116751588 A CN 116751588A
- Authority
- CN
- China
- Prior art keywords
- near infrared
- luminescent material
- scp
- inp
- grinding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- -1 rare earth ions Chemical class 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 46
- 238000000227 grinding Methods 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000012271 agricultural production Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- 238000006862 quantum yield reaction Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 description 39
- 229910052804 chromium Inorganic materials 0.000 description 27
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 20
- 238000005245 sintering Methods 0.000 description 15
- 229910052779 Neodymium Inorganic materials 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 229910052593 corundum Inorganic materials 0.000 description 13
- 239000010431 corundum Substances 0.000 description 13
- 238000000295 emission spectrum Methods 0.000 description 13
- 238000011049 filling Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 238000010532 solid phase synthesis reaction Methods 0.000 description 13
- 239000012856 weighed raw material Substances 0.000 description 13
- 229910052777 Praseodymium Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 238000000695 excitation spectrum Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000012984 biological imaging Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003333 near-infrared imaging Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7777—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7709—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7737—Phosphates
-
- 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
- C09K11/7756—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing neodynium
-
- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Landscapes
- 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 invention discloses a near infrared luminescent material, a preparation method thereof and an LED light source containing the luminescent material, and belongs to the technical field of fluorescent materials. The chemical composition of the luminescent material is represented by chemical formula MP 3 O 9 ：xCr 3+ ,yLn 3+ Wherein the M element is selected from one or more of Sc, in, V, fe and trivalent rare earth ions; the Ln element is selected from one or more of Yb, pr, nd, eu, sm, dy and other rare earth ions, cr 3+ And x is more than or equal to 0.01mol% and less than or equal to 100mol%, and y is more than or equal to 0.01mol% and less than or equal to 100mol% for luminescent center ions. The near infrared luminescent material has higher luminescence stability and luminescence quantum yield.
Description
The invention belongs to the field of luminescent materials, and particularly relates to a luminescent material with broadband near infrared emission, a preparation method thereof and an LED light source containing the luminescent material.
Background
With the continuous development of science and technology, the near infrared spectrum technology and the near infrared imaging technology have great effects on the aspects of food detection, biological detection, medical treatment and the like; along with the increase of life demands of people, the demand of portable detection equipment is larger and larger. The near infrared LED chip emits in a narrow band, the detection effect is difficult to achieve without the chip with characteristic wave bands, and the cost of the near infrared LED chip is high. The LED light source (pc-LED) converted by the fluorescent powder can obtain a wider spectrum and has the advantages of small volume, low cost, high efficiency, energy conservation and the like. And the blue light chip technology is mature, so that the pc-LED with good performance can be obtained only by obtaining the near infrared fluorescent powder with good thermal stability, wide emission spectrum and high quantum efficiency.
With the increasing demand of near infrared light sources, cr in recent years 3+ Doped near infrared fluorescent materials have many reports, and at present, cr is reported 3+ Near infrared materials, in particular Cr, as disclosed in the prior art 3+ In the doped near infrared fluorescent material, the near infrared luminescent material which can be effectively excited by a blue light source or a red light source and generates stronger near infrared broad spectrum emission and has good fluorescence heat stability is not fully developed. There is a report that Chinese patent CN107338046A discloses a MAl 12 O 19 xTi near infrared fluorescent powder, M is one or two of Ca and Sr, can be excited by 400-600nm light, emits 650-850nm red light and near infrared light, but has narrower emission spectrum and lower emission intensity; chinese patent CN103194232A discloses a near infrared fluorescent emission material excited by broadband ultraviolet-visible light, and a preparation method and application thereof, wherein the chemical formula of the fluorescent emission material is Y 1-x-z M z Cr x Yb y Al 3-y (BO 3 ) 4 Wherein M is Bi 3+ And La (La) 3+ One or two of 0<x≤0.2，0<y is less than or equal to 0.2, z is less than or equal to 0 and less than or equal to 0.2, the excitation wavelength of the fluorescent material is 350-650nm, the emission spectrum range is 900-1100nm, and the emission spectrum range is narrower. Ca 3 Sc 2 Si 3 O 12 :Ce 3+ ,Nd 3+ Preparation and luminescence Properties of near-infrared phosphor (silicate journal, volume 38, 10 of 2010) it is believed that phosphor Ca under blue excitation 3 Sc 2 Si 3 O 12 :Ce 3 + ,Nd 3+ Can generate near infrared luminescence between 800 and 1100nm, and has lower luminous intensity. Non-patent document Achieving an ultra-broadband infrared emission through efficient energy transfer in LiInP 2 O 7 :Cr 3+ ,Yb 3+ Phor under 460nm excitation, cr 3+ 、Yb 3+ Broad peaks with emission spectrum in 700-1100nm under co-doping, but the thermal stability is not good, and the method is not suitable for device encapsulation.
In summary, the material has a great effect in emitting near infrared light with a wavelength longer than 850nm, and the thermal stability and luminous efficiency are correspondingly reduced with the increase of the wavelength, so that it is necessary to develop a broadband near infrared luminescent material which can be excited by blue light and has high luminous efficiency and good thermal stability. The luminescent material is used for preparing a near infrared LED device converted by fluorescent powder, so that the luminescent material can be used in the detection field of near infrared detection technology.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a near infrared luminescent material, a preparation method thereof and a luminescent device containing the material.
< luminescent Material >
The invention provides a near infrared luminescent material, which comprises a compound with a chemical formula of MP 3 O 9 ：xCr 3+ ,yLn 3+ Wherein
The M element is selected from one or more of Sc, in, V, fe or trivalent rare earth ions;
the Ln element is one or more of Yb, nd, pr, eu, dy, sm and other rare earth ions,
Cr 3+ ln is a luminescent center ion 3+ Is sensitized with ions, wherein
0.01mol％≤x≤100mol％，0.01mol％≤y≤100mol％，
According to an embodiment of the invention, cr is preferred 3+ The concentration of (2) is 0.01mol% or more and x or less than 0.12mol% or less, preferably Ln 3+ The concentration of x is more than or equal to 0.03mol percent and less than or equal to 0.12mol percent.
According to an embodiment of the inventionThe luminescent material may have a chemical composition of ScP 3 O 9 :Cr 3+ ,Yb 3+ 、ScP 3 O 9 :Cr 3+ ,Nd 3+ 、ScP 3 O 9 :Cr 3+ ,Pr 3+ 、ScP 3 O 9 :Cr 3+ ,Eu 3+ 、ScP 3 O 9 :Cr 3+ ,Pr 3+ ,Nd 3+ 、ScP 3 O 9 :Cr 3+ ,Pr 3+ ,Yb 3+ 、ScP 3 O 9 :Cr 3+ ,Sm 3+ ,Eu 3+ 、ScP 3 O 9 :Cr 3+ ,Dy 3+ ,Eu 3+ 、ScP 3 O 9 :Cr 3+ ,Dy 3+ ,Sm 3+ 、VP 3 O 9 :Cr 3+ ,Yb 3+ 、VP 3 O 9 :Cr 3+ ,Nd 3+ 、VP 3 O 9 :Cr 3+ ,Pr 3+ 、VP 3 O 9 :Cr 3+ ,Eu 3+ 、VP 3 O 9 :Cr 3+ ,Pr 3+ ,Nd 3+ 、VP 3 O 9 :Cr 3+ ,Pr 3 + ,Yb 3+ 、VP 3 O 9 :Cr 3+ ,Sm 3+ ,Eu 3+ 、VP 3 O 9 :Cr 3+ ,Sm 3+ ,Dy 3+ 、VP 3 O 9 :Cr 3+ ,Dy 3+ ,Eu 3+ 、InP 3 O 9 :Cr 3+ ,Yb 3+ 、InP 3 O 9 :Cr 3+ ,Nd 3+ 、InP 3 O 9 :Cr 3+ ,Pr 3+ 、InP 3 O 9 :Cr 3+ ,Eu 3+ InP 3 O 9 :Cr 3+ ,Pr 3+ ,Yb 3+ 、InP 3 O 9 :Cr 3+ ,Pr 3 + ,Nd 3+ 、InP 3 O 9 :Cr 3+ ,Dy 3+ ,Sm 3+ 、InP 3 O 9 :Cr 3+ ,Dy 3+ ,Eu 3+ 、InP 3 O 9 :Cr 3+ ,Sm 3+ ,Eu 3+ 、FeP 3 O 9 :Cr 3+ ,Yb 3 + 、FeP 3 O 9 :Cr 3+ ,Nd 3+ 、FeP 3 O 9 :Cr 3+ ,Pr 3+ 、FeP 3 O 9 :Cr 3+ ,Eu 3+ 。
According to an embodiment of the invention, the luminescent material is capable of being excited under blue light, emitting near infrared light with a wavelength of 650-1300nm, with a peak value in the range of 850-950 nm.
< preparation method of luminescent Material >
The invention provides a preparation method of near infrared fluorescent powder, which comprises the following steps:
step one, MP according to the chemical formula 3 O 9 :xCr 3+ ,yLn 3+ Weighing M-element-containing compound, P-element-containing compound, cr-element-containing compound and Ln-element-containing compound. The obtained compound was mixed and ground to obtain a mixture.
And step two, presintering the obtained mixture at low temperature to obtain a presintering product.
And thirdly, performing first calcination on the presintered product obtained in the second step, grinding later, performing second calcination, taking out a sample, and performing aftertreatment to obtain the near infrared luminescent material.
According to an embodiment of the invention, in step one, the M-containing compound is not particularly required. Preferred sources of M are selected from the group consisting of oxides containing M elements, hydroxides containing M elements, carbonates containing M, nitrates containing M. Exemplary, the oxide containing M element is Sc 2 O 3 、In 2 O 3 、V 2 O 5 。
According to an embodiment of the present invention, in the first step, the P-source-containing compound is selected from one or more of a P-element-containing phosphate and a P-element-containing oxide, preferably monoammonium phosphate and diammonium phosphate.
According to an embodiment of the present invention, in the first step, the Cr-containing compound is selected from the group consisting of a Cr-containing carbonate, a Cr-containing oxide, and a Cr-containing nitrateOne or more of a salt and a halide containing Cr element, preferably Cr 2 O 3 、CrF 3 。
According to an embodiment of the present invention, in the first step, the Ln-containing compound is selected from the group consisting of an Ln-containing oxide, an Ln-containing hydroxide, an Ln-containing nitrate, and an Ln-containing halide. Preferably Yb 2 O 3 、Nd 2 O 3 、Pr 2 O 3 、Eu 2 O 3 、Dy 2 O 3 、Sm 2 O 3 。
According to an embodiment of the invention, in step one, the luminescent material MP 3 O 9 ：xCr 3+ ,yLn 3+ The purity of the raw materials is more than or equal to 99 percent, preferably more than or equal to 99.5 percent.
According to an embodiment of the present invention, in step one, MP is represented by formula 3 O 9 ：xCr 3+ ,yLn 3+ The stoichiometric ratio of the respective elements is used to weigh the M element-containing compound, the P element-containing compound, the Cr element-containing compound, and the Ln element-containing compound, wherein the P source compound may be used in an appropriate excess amount, for example, 5 to 200wt.%.
According to the embodiment of the present invention, in the first step, the weighed M-containing compound, P-containing compound, cr-containing compound, ln-containing compound are mixed in a manner not particularly limited, and grinding equipment such as a mortar, a ball mill, a mixer, and the like can be used.
According to an embodiment of the present invention, in the first step, the pre-sintering is performed at a temperature lower than 250 ℃, and the pre-sintering atmosphere may be performed in air or an inert atmosphere.
According to an embodiment of the invention, in step two, the first and second calcination may be performed in air, an inert atmosphere or a reducing atmosphere. Such as nitrogen, argon, etc.; the reducing atmosphere is, for example, (5-15% by volume) H 2 And (95-85 v%) N 2 A mixed gas, or an atmosphere containing carbon powder.
According to an embodiment of the present invention, in the second step, the conditions of the first calcination include: the temperature is 300-900 ℃, preferably 400-800 ℃, and the calcination time is 1-30h, preferably 8-15h. The conditions for the second calcination include: the temperature is 800-1400 ℃, preferably 1000-1300 ℃, and the calcination time is 1-30h, preferably 8-15h.
According to an embodiment of the present invention, in the second step, the number of times of calcination is at least two, for example, may be two, three or more times. And preferably the temperatures of each calcination are different from each other. More preferably, the temperature of each calcination is in an ascending trend. The calcined product of the previous time may be ground before the next calcination.
According to an embodiment of the present invention, in step three, the post-treatment includes grinding, washing, filtering, drying, and the like. Illustratively, the resulting product is ground, washed 1-3 times with deionized water, 1-2 times with absolute ethanol, filtered and oven dried at 60-100deg.C.
< LED light Source comprising luminescent Material >
The invention also provides an LED light source, which comprises at least one near infrared luminescent material.
Further, the invention provides an LED light source, which comprises a fluorescence conversion layer and an LED semiconductor chip, wherein the fluorescence conversion layer is arranged on the LED semiconductor chip, and the fluorescence conversion layer comprises at least one near infrared luminescent material.
According to an embodiment of the present invention, the fluorescent conversion layer is a layer including an encapsulation paste and a light emitting material, wherein the light emitting material is uniformly dispersed in the encapsulation material. The package can be made of organic materials such as epoxy resin, polycarbonate or silica gel, or inorganic materials such as boron oxide, potassium oxide, silicon dioxide, etc.; preferably silica gel. The amount of the encapsulating material is not particularly limited as long as it can be uniformly applied on the LED semiconductor chip according to operations known in the art.
According to an embodiment of the present invention, the fluorescent conversion layer is coated on an LED semiconductor chip for carrying the above-mentioned fluorescent conversion layer.
According to an embodiment of the present invention, the LED semiconductor chip is at least one of a blue LED chip and a red LED chip.
According to an embodiment of the present invention, the peak value of the blue LED chip is in the range of 400-500 nm.
According to an embodiment of the present invention, the peak value of the red LED chip is in the range of 590-680 nm.
According to an embodiment of the invention, the LED light source is a fluorescence conversion type near infrared LED device. Further, the fluorescence conversion type near infrared LED device is used in the fields of biological identification, sensing, food detection, medical detection, agricultural production or biological imaging and the like.
The invention has the beneficial effects that:
(1) The near infrared luminescent material with the broadband emission characteristic provided by the invention can be used as a light conversion material of a near ultraviolet LED chip, a blue light LED chip and a red light LED chip, realizes a high-efficiency stable broadband near infrared luminescent light source, solves the problem of narrow bandwidth of the existing infrared LEDs and infrared lasers, and can meet the requirements of the application of food detection, medical detection, agricultural production or biological imaging on the broadband infrared light source.
(2) The near infrared material of the invention adopts Cr 3+ As activator, ln 3+ As sensitizer, near infrared luminescence enhancement is realized, so that MP 3 O 9 :xCr 3+ ,yLn 3+ Compared with the material without sensitizer, the material has obviously improved luminous efficiency and thermal stability.
(3) The luminescent material provided by the invention has the advantages of simple preparation process, no pollution and low cost.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below.
Fig. 1 is an XRD pattern of a luminescent material prepared in example 1 of the present invention.
Fig. 2 is an excitation spectrum of the luminescent material prepared in example 1 of the present invention.
Fig. 3 is an emission spectrum of the luminescent material prepared in example 1 of the present invention.
Fig. 4 is an excitation spectrum of the luminescent material prepared in example 3 of the present invention.
Fig. 5 is an emission spectrum of the luminescent material prepared in example 3 of the present invention.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1: scP (ScP) 3 O 9 ：6％Cr 3+ ,3％Nd 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ ,3％Nd 3+ The stoichiometric ratio of the various elements in the water scale is used for weighing Sc 2 O 3 0.1569g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, nd 2 O 3 0.0126g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 600 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 6 hours at 1185 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Example 2: scP (ScP) 3 O 9 ：6％Cr 3+ ,5％Nd 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ ,5％Nd 3+ The stoichiometric ratio of the various elements in the water scale is used for weighing Sc 2 O 3 0.1534g of NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, nd 2 O 3 0.0210g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 600 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2h at 200 ℃ in a baking oven, cooling, taking out, putting into a box-type furnace, sintering for 6h at 1185 ℃, grinding the obtained sample after the calcination is finished, and obtaining the near infrared luminescent material
Example 3: scP (ScP) 3 O 9 ：6％Cr 3+ ,3％Pr 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ ,3％Pr 3+ The stoichiometric ratio of the various elements in the water scale is used for weighing Sc 2 O 3 0.1569g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, pr 2 O 3 0.0124g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 600 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 6 hours at 1150 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material. .
Example 4: scP (ScP) 3 O 9 ：6％Cr 3+ ,5％Pr 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ ,5％Pr 3+ The stoichiometric ratio of the various elements in the water scale is used for weighing Sc 2 O 3 0.1534g of NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, pr 2 O 3 0.0206g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 600 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 6 hours at 1150 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Example 5: scP (ScP) 3 O 9 ：6％Cr 3+ ,3％Nd 3+ ,3％Pr 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ ,3％Nd 3+ ,3％Pr 3+ The stoichiometric ratio of the various elements in the water scale is used for weighing Sc 2 O 3 0.1517g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, pr 2 O 3 0.0124g, nd 2 O 3 0.0126g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 600 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 6 hours at 1250 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Example 6: VP 3 O 9 ：6％Cr 3+ ,3％Pr 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ ,3％Nd 3+ ,3％Pr 3+ The stoichiometric ratio of the various elements in the (B) is used for weighing V 2 O 5 0.2069g of NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, pr 2 O 3 0.0124g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling the mixture into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 500 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 10 hours at 1000 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Example 7: VP 3 O 9 ：6％Cr 3+ ,3％Yb 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ ,3％Nd 3+ ,3％Pr 3+ The stoichiometric ratio of the various elements in the (B) is used for weighing V 2 O 5 0.2069g of NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g Yb 2 O 3 0.0148g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling the mixture into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 500 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 10 hours at 1050 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Example 8: inP (indium phosphide) 3 O 9 ：6％Cr 3+ ,3％Nd 3+ Preparation of fluorescent materials
The embodiment adopts a high-temperature solid phase method for synthesis, and firstly, the method is carried out according to the chemical formula InP 3 O 9 ：6％Cr 3+ ,3％Nd 3+ In is weighed In stoichiometric ratio of various elements In the furnace 2 O 3 0.3518g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, nd 2 O 3 0.0126g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling the mixture into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 500 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering at 1100 ℃ for 8 hours, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Example 9: inP (indium phosphide) 3 O 9 ：6％Cr 3+ ,3％Dy 3+ Preparation of fluorescent materials
The embodiment adopts a high-temperature solid phase method for synthesis, and firstly, the method is carried out according to the chemical formula InP 3 O 9 ：6％Cr 3+ ,3％Nd 3+ In is weighed In stoichiometric ratio of various elements In the furnace 2 O 3 0.3518g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g Dy 2 O 3 0.0140g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling the mixture into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 500 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering at 1100 ℃ for 8 hours, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Example 10: inP (indium phosphide) 3 O 9 :6％Cr 3+ ,3％Eu 3+ Preparation of fluorescent materials
The embodiment adopts a high-temperature solid phase method for synthesis, and firstly, the method is carried out according to the chemical formula InP 3 O 9 :6％Cr 3+ ,3％Nd 3+ In is weighed In stoichiometric ratio of various elements In the furnace 2 O 3 0.3158g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, eu 2 O 3 0.0132g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling the mixture into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 500 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering at 1100 ℃ for 8 hours, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Comparative example 1: scP (ScP) 3 O 9 :6％Cr 3+ Preparation of fluorescent powder
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ The stoichiometric ratio of the various elements in the water scale is used for weighing Sc 2 O 3 0.1620g of NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 600 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 6 hours at 1250 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Comparative example 2: inP (indium phosphide) 3 O 9 :7％Cr 3+ Preparation of fluorescent powder
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 ：6％Cr 3+ In is weighed In stoichiometric ratio of various elements In the furnace 2 O 3 0.3227g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0133g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 500 ℃ in air atmosphere, cooling to room temperature,grinding is carried out again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering at 1100 ℃ for 8 hours, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
Comparative example 3: scP (ScP) 3 O 9 :6％Cr 3+ ,3％Nd 3+ ,3％Pr 3+ Preparation of fluorescent materials
The present example uses a high temperature solid phase method, first according to the chemical formula ScP 3 O 9 :6％Cr 3+ ,3％Nd 3+ ,3％Pr 3+ The stoichiometric ratio of the various elements in the water scale is used for weighing Sc 2 O 3 0.1517g, NH 4 H 2 PO 4 1.0352g (20 wt.% excess), cr 2 O 3 0.0114g, pr 2 O 3 0.0124g, nd 2 O 3 0.0126g. Grinding the weighed raw materials in a mortar, mixing uniformly, filling into a corundum crucible, preserving heat for 2 hours at 200 ℃ in an oven, cooling, taking out, putting into a box-type furnace, calcining for 3 hours at 600 ℃ in an air atmosphere, cooling to room temperature, and grinding again. Then preserving heat for 2 hours at 200 ℃ in the oven again, cooling, taking out, putting into a box-type furnace, sintering for 6 hours at 1250 ℃, and grinding the obtained sample after the calcination is finished to obtain the near infrared luminescent material.
The phases of the samples of examples and comparative examples were analyzed using an X-ray powder diffractometer (D8 advanced, germany).
The excitation and emission spectra of the samples were measured with a FLS980 (Edinburgh instruments) fluorescence spectrometer, and the thermal stability of the materials was evaluated by testing the temperature-varying emission spectra of the materials in combination with a 77-600K temperature-varying stage.
The luminescent quantum yield of the materials was tested by fiber coupling to integrating spheres using a fiber spectrometer (ATP 5020R).
XRD analysis of the samples synthesized by the solid phase reaction showed pure phases. For example, the XRD diffractogram of the near infrared luminescent material prepared in example 1 is shown in fig. 1; as can be seen from FIG. 1, the luminescent material is a pure phase ScP 3 O 9 。
The excitation and emission spectra of the samples were measured with an FLS980 (Edinburgh instruments) fluorescence spectrometer. The excitation spectrum of the luminescent material of example 1 is shown in FIG. 2, and the excitation spectrum of the luminescent material comprises three effective excitation bands of 250-350nm, 420-580nm and 600-800nm respectively; the emission spectrum of the luminescent material is shown in fig. 3, and it can be seen that the emission spectrum of the luminescent material covers 800-1100nm, i.e. has near infrared broadband emission properties. FIG. 4 shows the excitation spectrum of the luminescent material according to example 3 of the present invention, and it can be seen from FIG. 4 that the excitation spectrum ranges from 250 to 350nm, from 420 to 550nm, and from 600 to 800nm under 885nm excitation. FIG. 5 shows the emission spectrum of the luminescent material prepared in example 3 of the present invention, with an emission wavelength of 800-1100nm. It is shown that the material has a broad band emission.
In addition, the near infrared luminescent materials prepared in examples 1 to 9 and comparative examples 1 and 2 were tested for luminescence quantum yield and thermal stability, and the test results are shown in Table 1, and compared with comparative examples 1 and 2, the near infrared luminescent materials prepared in examples were prepared by various rare earth ions and Cr 3+ And the ion co-doping constructs an energy transfer channel between the ion co-doping and the ion co-doping, reduces the probability of non-radiative transition, and obtains higher luminous quantum yield. In addition, through the co-doping of a plurality of rare earth ions, competition exists between the energy transfer between ions at high temperature and the non-radiative transition caused by temperature rise, so that the material obtains better fluorescence thermal stability. In comparison with example 1 and example 2, it was found that the doping concentration of rare earth ions should not be too high, and that a second phase is easily generated after the doping is too high, which affects the luminous efficiency of the material. Example 5 compared with comparative example 3, it was found that the secondary calcination was effective in improving the luminous efficiency of the material, which was mainly that the secondary calcination was a more sufficient reaction of the material and the grain growth of the material particles was more complete. The near infrared luminescent material prepared by the invention has obviously higher luminous quantum yield and better thermal stability.
TABLE 1
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, should be included in the scope of the present invention.
Claims (9)
1. A near infrared luminescent material, characterized in that the chemical composition of the luminescent material is represented by the chemical formula MP 3 O 9 ：xCr 3+ ,yLn 3+ The representation, wherein,
the M element is selected from one or more of Sc, in, V, fe or trivalent rare earth ions;
the Ln element is one or more of Yb, nd, pr, eu, dy, sm and other rare earth ions,
Cr 3+ ln is a luminescent center ion 3+ Is sensitized with ions, wherein
0.01mol％≤x≤100mol％，0.01mol％≤y≤100mol％。
2. According to an embodiment of the present invention, the luminescent material may have a chemical composition of ScP 3 O 9 :Cr 3+ ,Yb 3+ 、ScP 3 O 9 :Cr 3+ ,Nd 3+ 、ScP 3 O 9 :Cr 3+ ,Pr 3+ 、ScP 3 O 9 :Cr 3+ ,Eu 3+ 、ScP 3 O 9 :Cr 3+ ,Pr 3+ ,Nd 3+ 、ScP 3 O 9 :Cr 3+ ,Pr 3+ ,Yb 3+ 、ScP 3 O 9 :Cr 3+ ,Sm 3+ ,Eu 3+ 、ScP 3 O 9 :Cr 3+ ,Dy 3+ ,Eu 3+ 、ScP 3 O 9 :Cr 3+ ,Dy 3+ ,Sm 3+ 、VP 3 O 9 :Cr 3+ ,Yb 3+ 、VP 3 O 9 :Cr 3+ ,Nd 3+ 、VP 3 O 9 :Cr 3+ ,Pr 3+ 、VP 3 O 9 :Cr 3+ ,Eu 3+ 、VP 3 O 9 :Cr 3+ ,Pr 3+ ,Nd 3+ 、VP 3 O 9 :Cr 3+ ,Pr 3+ ,Yb 3+ 、VP 3 O 9 :Cr 3+ ,Sm 3+ ,Eu 3+ 、VP 3 O 9 :Cr 3+ ,Sm 3+ ,Dy 3+ 、VP 3 O 9 :Cr 3+ ,Dy 3+ ,Eu 3+ 、InP 3 O 9 :Cr 3+ ,Yb 3+ 、InP 3 O 9 :Cr 3+ ,Nd 3+ 、InP 3 O 9 :Cr 3+ ,Pr 3+ 、InP 3 O 9 :Cr 3+ ,Eu 3+ InP 3 O 9 :Cr 3+ ,Pr 3+ ,Yb 3+ 、InP 3 O 9 :Cr 3+ ,Pr 3+ ,Nd 3+ 、InP 3 O 9 :Cr 3+ ,Dy 3+ ,Sm 3+ 、InP 3 O 9 :Cr 3+ ,Dy 3+ ,Eu 3+ 、InP 3 O 9 :Cr 3+ ,Sm 3+ ,Eu 3+ 、FeP 3 O 9 :Cr 3+ ,Yb 3+ 、FeP 3 O 9 :Cr 3+ ,Nd 3+ 、FeP 3 O 9 :Cr 3+ ,Pr 3+ 、FeP 3 O 9 :Cr 3+ ,Eu 3+ 。
The near infrared luminescent material is characterized in that the luminescent material is capable of being excited by blue light.
3. The method for preparing near infrared light emitting material according to claim 1 or 2, characterized by comprising the steps of:
step one, MP according to chemical formula 3 O 9 ：xCr 3+ ,yLn 3+ The stoichiometric ratio of each element in the mixture is that M element-containing compound, P element-containing compound, cr element-containing compound and Ln element-containing compound are mixed to obtain a mixture;
step two, presintering the mixture to obtain a presintering product;
and thirdly, calcining the presintered product obtained in the second step for the first time, grinding later, calcining for the second time, taking out the sample, and performing aftertreatment to obtain the near infrared luminescent material.
4. A process according to claim 3, wherein in step one, the M-containing compound is not particularly required. Preferred sources of M are selected from the group consisting of oxides containing M elements, hydroxides containing M elements, carbonates containing M. More preferably the oxide containing M element is Sc 2 O 3 、In 2 O 3 、V 2 O 5 。
Preferably, in the first step, the P-source-containing compound is one or more selected from a phosphate containing P element and an oxide containing P element, and more preferably, monoammonium phosphate and diammonium phosphate.
Preferably, in the first step, the Cr-containing compound is selected from one or more of a Cr-containing carbonate, a Cr-containing oxide, a Cr-containing nitrate and a Cr-containing halide, more preferably Cr 2 O 3 、CrF 3 。
Preferably, in the first step, the Ln-containing compound is selected from the group consisting of an oxide containing Ln element, a hydroxide containing Ln element, a nitrate containing Ln element, and a halide containing Ln. Preferably Yb 2 O 3 、Nd 2 O 3 、Pr 2 O 3 、Eu 2 O 3 、Dy 2 O 3 、Sm 2 O 3 。
5. The method according to claim 3 or 4, wherein in the second step, the pre-firing is performed at a temperature lower than 250 ℃, and the pre-firing atmosphere is performed in air or an inert atmosphere.
Preferably, in step two, the calcination is performed in air, an inert atmosphere or a reducing atmosphere; the temperature of the first calcination is 300-900 ℃, preferably 400-800 ℃, and the calcination time is 1-30h, preferably 8-15h. The conditions for the second calcination include: the temperature is 800-1400 ℃, preferably 1000-1300 ℃, and the calcination time is 1-30h, preferably 8-15h.
6. The method according to any one of claims 3 to 5, wherein in step three, the post-treatment comprises washing, grinding, filtering, drying, and the like.
Preferably, in the third step, the post-treatment includes grinding, washing, filtering, drying, and the like. More preferably, the obtained product is ground, washed 1-3 times with deionized water, 1-2 times with absolute ethanol, filtered and dried in an oven at 60-100 ℃.
7. An LED light source comprising at least one near infrared luminescent material as claimed in any one of claims 1 or 2.
8. The LED light source of claim 6, wherein the LED light source comprises a fluorescent conversion layer and an LED semiconductor chip, and the fluorescent conversion layer is mounted on the LED semiconductor chip,
wherein the fluorescent conversion layer comprises at least one near infrared light emitting material according to any one of claims 1 or 2;
preferably, the LED semiconductor chip is at least one selected from a blue LED chip and a red LED chip.
9. Use of the LED light source of claim 7 or 8 in the fields of biological identification, sensing, food detection, medical detection, agricultural production or bioimaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310769509.1A CN116751588B (en) | 2023-06-28 | 2023-06-28 | Near infrared luminescent material, preparation method thereof and LED light source containing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310769509.1A CN116751588B (en) | 2023-06-28 | 2023-06-28 | Near infrared luminescent material, preparation method thereof and LED light source containing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116751588A true CN116751588A (en) | 2023-09-15 |
| CN116751588B CN116751588B (en) | 2024-05-14 |
Family
ID=87947643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310769509.1A Active CN116751588B (en) | 2023-06-28 | 2023-06-28 | Near infrared luminescent material, preparation method thereof and LED light source containing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116751588B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200326277A1 (en) * | 2019-04-12 | 2020-10-15 | Lumileds Holding B.V. | Novel nir broadband emitting phosphors for infrared spectroscopy |
| CN113444524A (en) * | 2020-03-25 | 2021-09-28 | 亮锐有限责任公司 | IR-emitting pyroxene phosphor, and light emitting device using the same |
| US20210305468A1 (en) * | 2020-03-25 | 2021-09-30 | Lumileds Llc | Ir emitting pyroxene phosphors and light emitting device using the same |
| CN114410302A (en) * | 2021-12-15 | 2022-04-29 | 有研稀土新材料股份有限公司 | Near-infrared fluorescent powder and optical device thereof |
| CN115746847A (en) * | 2022-10-20 | 2023-03-07 | 兰州大学 | Preparation method of metal ion doped metaphosphate near-infrared luminescent material |
| CN116200194A (en) * | 2021-11-30 | 2023-06-02 | 厦门稀土材料研究所 | Near infrared luminescent material, preparation method thereof and LED light source containing luminescent material |
-
2023
- 2023-06-28 CN CN202310769509.1A patent/CN116751588B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200326277A1 (en) * | 2019-04-12 | 2020-10-15 | Lumileds Holding B.V. | Novel nir broadband emitting phosphors for infrared spectroscopy |
| CN113811590A (en) * | 2019-04-12 | 2021-12-17 | 亮锐有限责任公司 | Novel NIR broadband emitting phosphors for infrared spectroscopy |
| CN113444524A (en) * | 2020-03-25 | 2021-09-28 | 亮锐有限责任公司 | IR-emitting pyroxene phosphor, and light emitting device using the same |
| US20210305468A1 (en) * | 2020-03-25 | 2021-09-30 | Lumileds Llc | Ir emitting pyroxene phosphors and light emitting device using the same |
| CN116200194A (en) * | 2021-11-30 | 2023-06-02 | 厦门稀土材料研究所 | Near infrared luminescent material, preparation method thereof and LED light source containing luminescent material |
| CN114410302A (en) * | 2021-12-15 | 2022-04-29 | 有研稀土新材料股份有限公司 | Near-infrared fluorescent powder and optical device thereof |
| CN115746847A (en) * | 2022-10-20 | 2023-03-07 | 兰州大学 | Preparation method of metal ion doped metaphosphate near-infrared luminescent material |
Non-Patent Citations (1)
| Title |
|---|
| 蒋立朋等: "YAG:Ce3+荧光粉的制备工艺及发光性能研究", 长春理工大学学报(自然科学版), no. 5, 31 October 2017 (2017-10-31), pages 83 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116751588B (en) | 2024-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110857389B (en) | Near-infrared fluorescent powder and light-emitting device containing same | |
| JP7062693B6 (en) | Near-infrared light emitting material and light emitting device made of the material | |
| CN111117618B (en) | Broadband near-infrared luminescent material and preparation method and application thereof | |
| CN112342021A (en) | Near-infrared broadband emission luminescent material, preparation method thereof and luminescent device comprising material | |
| CN116200194B (en) | Near infrared luminescent material, preparation method thereof and LED light source containing luminescent material | |
| KR101717241B1 (en) | Red light-emitting nitride material, and light-emitting part and light-emitting device comprising same | |
| CN114590831B (en) | LaSi 2 N 3 O crystal and fluorescent powder and preparation method thereof | |
| CN110591711B (en) | Gallate red fluorescent powder for white light LED and preparation method thereof | |
| CN112625683A (en) | Germanate type red fluorescent powder and preparation method thereof | |
| CN115340869B (en) | Orange luminescent material, preparation method thereof and white light LED | |
| CN116751588B (en) | Near infrared luminescent material, preparation method thereof and LED light source containing material | |
| CN111778021B (en) | High-luminescence thermal-stability bluish violet luminescent material and preparation method and application thereof | |
| CN110272740B (en) | Zero-doped rare earth borate red fluorescent powder, preparation and application thereof in L ED field | |
| CN111978956A (en) | Orange light long afterglow fluorescent powder and preparation method thereof | |
| CN116987504B (en) | Luminescent material, preparation method thereof and luminescent device comprising luminescent material | |
| CN111040762A (en) | Single-matrix chromaticity-adjustable luminescent material and preparation method and application thereof | |
| CN116396753B (en) | Single-doped nitrogen oxide cold white light fluorescent powder | |
| CN115322783B (en) | Gadolinium metaborate fluorescent material co-doped with bismuth ions and/or rare earth ions and synthesis method | |
| CN114806559B (en) | Eu (Eu) 2+ Activated ultra-wideband visible-near infrared luminescent material, preparation method and application | |
| CN116656359B (en) | Tungsten titanate matrix material for rare earth fluorescent powder, fluorescent material and preparation method of fluorescent material | |
| CN114854412B (en) | Near ultraviolet excited narrow-band deep blue luminescent material and preparation method thereof | |
| CN114196402B (en) | Eu-doped ultrahigh chromogenic borophosphate and preparation method and application thereof | |
| CN108048089A (en) | A kind of burst of ultraviolel white light LEDs multicolor luminous fluorescent powder and preparation method thereof | |
| CN107987833B (en) | Nitride luminescent material and luminescent device comprising same | |
| CN110951489B (en) | Europium-activated silicate blue-light fluorescent powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |