CN116875308A - Luminescent material, preparation method thereof and LED light source - Google Patents
Luminescent material, preparation method thereof and LED light source Download PDFInfo
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- CN116875308A CN116875308A CN202310873262.8A CN202310873262A CN116875308A CN 116875308 A CN116875308 A CN 116875308A CN 202310873262 A CN202310873262 A CN 202310873262A CN 116875308 A CN116875308 A CN 116875308A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- 239000011651 chromium Substances 0.000 claims description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 229910052732 germanium Inorganic materials 0.000 claims description 16
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- -1 oxide Chemical compound 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 56
- 238000004020 luminiscence type Methods 0.000 abstract description 17
- 238000000227 grinding Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 description 49
- 230000005284 excitation Effects 0.000 description 23
- 239000003570 air Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 13
- 238000002284 excitation--emission spectrum Methods 0.000 description 13
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 12
- 239000010431 corundum Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals
- C09K11/717—Aluminates; Silicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- 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 relates to the technical field of LED light source materials, and particularly provides a luminescent material, a preparation method thereof and an LED light source. The luminescent material of the invention is shown in the formula 1, ca 1‑x Ge 4‑y‑z (PO 4 ) 6 xM, yR, zCr formula 1; in the formula 1, M is selected from one or more of Mg, sr, ba, zn; r is selected from one or more of Sn, si, zr, ti; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 4,0.0001, and z is more than or equal to 1. Compared with the prior art, the luminescent material has the luminescence peak range of 650-850 nm, can be effectively excited by ultraviolet light and blue light, and has higher generated near infrared luminescence intensity; meanwhile, the luminescent material has the advantages of simple preparation process, low raw material cost, stable chemical property, fluffiness, easy grinding, no radioactivity and no harm to the environment.
Description
Technical Field
The invention relates to the technical field of LED light source materials, in particular to a luminescent material, a preparation method thereof and an LED light source.
Background
The near infrared light source can be applied to modern agricultural illumination, food safety detection and security protectionMonitoring, photovoltaic and spectroscopic analysis techniques. The near infrared fluorescent powder conversion type LED light source is the preferred light source because of the advantages of low cost, compact structure, high radiation power, adjustable emission spectrum and the like. Therefore, the development of near infrared luminescent materials with excellent luminescence properties is a key to realizing efficient near infrared LED light sources. Cr (Cr) 3+ The activated near infrared fluorescent powder is paid attention to because of the advantages of easy synthesis, high matching degree of an excitation spectrum and a blue light LED chip, high internal quantum efficiency, adjustable emission of ultra-wideband and the like. The domestic and international markets have great application demands on near infrared luminescent materials, and development of near infrared luminescent materials with excellent performance is needed at present.
Disclosure of Invention
In view of the above, the invention aims to provide a luminescent material, a preparation method thereof and an LED light source, wherein the luminescent peak range of the luminescent material is 650-850 nm, the luminescent material can be effectively excited by ultraviolet light and blue light, and the generated near infrared luminous intensity is higher; meanwhile, the luminescent material has the advantages of simple preparation process, low raw material cost, stable chemical property, fluffiness, easy grinding, no radioactivity and no harm to the environment.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the luminescent material as shown in figure 1,
Ca 1-x Ge 4-y-z (PO 4 ) 6 xM, yR, zCr formula 1;
in the formula 1, M is selected from one or more of Mg, sr, ba, zn;
r is selected from one or more of Sn, si, zr, ti;
0≤x≤1，0≤y≤4，0.0001≤z≤1。
in the luminescent material, chromium is trivalent chromium ion, M is divalent ion, and R is tetravalent ion.
In the formula 1, M is selected from one or more of Mg, sr and Zn;
r is selected from one or more of Sn, si and Ti;
0≤x≤0.5，0≤y≤1，0.0001≤z≤0.1。
in formula 1 of the present invention, M is Mg or Zn, preferably Zn;
r is selected from Si, sn or Ti, preferably Si or Sn, and more preferably Sn;
x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.1,0.005, and z is more than or equal to 0.03; preferably, x=0, y= 0,0.005.ltoreq.z.ltoreq.0.03.
In the present invention, the luminescent material has the chemical formula CaGe 3.99 (PO 4 ) 6 :0.01Cr、CaGe 4 (PO 4 ) 6 :0.01Cr、CaGe 3.59 (PO 4 ) 6 :0.01Cr、CaGe 3.99 (PO 4 ) 6 :0.05Cr、Ca 0.999 Ge 3.989 (PO 4 ) 6 :0.001Zn,0.001Sn,0.01Cr、Ca 0.98 Ge 3.99 (PO 4 ) 6 :0.01Cr,0.02Mg、Ca 0.99 Ge 3.98 (PO 4 ) 6 :0.01Cr,0.01Mg,0.01Ti、CaGe 3.89 (PO 4 ) 6 :0.01Cr,0.1Sn、CaGe 3.94 (PO 4 ) 6 One or more of 0.01Cr and 0.05 Si.
The invention also provides a preparation method of the luminescent material, which comprises the following steps: mixing a calcium source, a germanium source, a chromium source, a phosphorus source, an M source and an R source, and heating to obtain a luminescent material shown in a formula 1;
the M source and R source are optionally added;
Ca 1-x Ge 4-y-z (PO 4 ) 6 xM, yR, zCr formula 1;
in the formula 1, M is selected from one or more of Mg, sr, ba, zn;
r is selected from one or more of Sn, si, zr, ti;
0≤x≤1，0≤y≤4，0.0001≤z≤1。
in the formula 1, M is selected from one or more of Mg, sr and Zn;
r is selected from one or more of Sn, si and Ti;
0≤x≤0.5，0≤y≤1，0.0001≤z≤0.1。
in formula 1 of the present invention, M is Mg or Zn, preferably Zn;
r is selected from Si, sn or Ti, preferably Si or Sn, and more preferably Sn;
x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0 and less than or equal to 0.1,0.005, and z is more than or equal to 0.03; preferably, x=0, y= 0,0.005.ltoreq.z.ltoreq.0.03.
In the present invention, the luminescent material has the chemical formula CaGe 3.99 (PO 4 ) 6 :0.01Cr、CaGe 4 (PO 4 ) 6 :0.01Cr、CaGe 3.59 (PO 4 ) 6 :0.01Cr、CaGe 3.99 (PO 4 ) 6 :0.05Cr、Ca 0.999 Ge 3.989 (PO 4 ) 6 :0.001Zn,0.001Sn,0.01Cr、Ca 0.98 Ge 3.99 (PO 4 ) 6 :0.01Cr,0.02Mg、Ca 0.99 Ge 3.98 (PO 4 ) 6 :0.01Cr,0.01Mg,0.01Ti、CaGe 3.89 (PO 4 ) 6 :0.01Cr,0.1Sn、CaGe 3.94 (PO 4 ) 6 One or more of 0.01Cr and 0.05 Si.
The present invention is not particularly limited to the mixing, and the calcium source, the germanium source, the chromium source, the phosphorus source, the M source and the R source may be mixed by a method well known to those skilled in the art.
After the mixing is completed, the heating includes: preheating the mixture at 400-500 ℃, cooling, and sintering the cooled mixture at 800-1500 ℃; the preheating time is 1-12 h, preferably 3-5 h; the sintering temperature is preferably 900-1200 ℃, more preferably 1000-1100 ℃, for 1-24 hours, preferably 3-12 hours, and most preferably 8-10 hours.
After the preheating is completed, the present invention preferably cools the resulting product; preferably cooling to room temperature; the cooling mode is natural cooling; the cooled product is preferably ground. After the sintering is completed, the present invention preferably cools the resulting product; preferably cooling to room temperature; the cooling mode is natural cooling; the cooled product is preferably ground.
In the invention, the molar ratio of the calcium source, the germanium source, the phosphorus source, the chromium source, the M source and the R source is (0.5-1.5): (3-5): (4-8): (0.001-0.1): (0-0.5), preferably (0.8-1.2): (3.5-4.5): (5-7): (0.001-0.005): (0-0.1).
In one embodiment of the invention, the molar ratio of the calcium source, the germanium source, the phosphorus source and the chromium source is 1:3.99:6:0.005.
in one embodiment of the present invention, the molar ratio of the calcium source, the germanium source, the phosphorus source, the chromium source, and the R source is 1:3.89:6:0.005:0.1.
in one embodiment of the present invention, the molar ratio of the calcium source, the germanium source, the phosphorus source, the chromium source, and the R source is 1:3.94:0.05:6:0.01.
in one embodiment of the invention, the molar ratio of the calcium source, the germanium source, the phosphorus source, the chromium source and the M source is 0.98:3.99:6:0.005:0.02.
in one embodiment of the invention, the molar ratio of the calcium source, the germanium source, the phosphorus source, the chromium source, the M source, and the R source is 0.99:3.98:6:0.005:0.01:0.01.
in one embodiment of the invention, the molar ratio of the calcium source, the germanium source, the phosphorus source and the chromium source is 1:3.59:6:0.005.
in one embodiment of the invention, the molar ratio of the calcium source, the germanium source, the phosphorus source and the chromium source is 1:3.99:6:0.05.
in the present invention, the chromium source comprises one or more of nitrate, phosphate, oxide, chloride of chromium, preferably Cr 2 O 3 ；
The calcium source comprises one or more of calcium oxide, carbonate and nitrate, preferably CaCO 3 ；
The germanium source comprises an oxide of germanium, preferably GeO 2 ；
The phosphorus source comprises an ammonium phosphate salt, preferably NH4H2PO4.
In the present invention, the M source includes one or more of an oxide, a carbonate, and a nitrate of an M element, preferably an oxide of an M element, and more preferably MgO;
the R source comprises one or more of oxide, carbonate and nitrate of R element, preferably oxide of R element, more preferably SiO 2 、SnO 2 Or TiO 2 。
In the present invention, the heating is performed in an atmosphere; the atmosphere comprises air, nitrogen, argon or a hydrogen-containing gas, preferably nitrogen or air.
The invention also provides the LED light source, which comprises the luminescent material. The LED light source of the invention also comprises a blue light chip.
The luminescent material Ca provided by the invention 1-x Ge 4-y-z (PO 4 ) 6 The invention relates to an xM, yR, zCr near infrared luminescent material which takes calcium germanium phosphate as a basic component, trivalent chromium ions as luminescent ions and divalent and tetravalent ions as co-doping. Compared with the prior art, the luminescent material has the luminescence peak range of 650-850 nm, can be effectively excited by ultraviolet light and blue light, and has higher generated near infrared luminescence intensity; meanwhile, the luminescent material has the advantages of simple preparation process, low raw material cost, stable chemical property, fluffiness, easy grinding, no radioactivity and no harm to the environment.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a luminescent material provided in example 1 of the present invention;
FIG. 2 is a graph showing the excitation emission spectrum of the luminescent material according to example 1 of the present invention;
fig. 3 is an emission spectrum of the luminescent materials provided in examples 1 and 12 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
Example 1
The raw material is CaCO 3 (analytical grade))、GeO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.99:6:0.005, the raw materials are weighed according to the proportion, the raw materials are evenly mixed and placed into a corundum crucible, presintering is carried out for 5 hours at 400 ℃, grinding is carried out again after cooling, the raw materials are placed into the crucible, then the crucible is placed into a high-temperature furnace, roasting is carried out for 10 hours at 1050 ℃ in air atmosphere, and the raw materials are naturally cooled to room temperature, thus obtaining the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.99 (PO 4 ) 6 0.01Cr, as shown in figure 1; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435nm, as shown in fig. 2; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 2
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.99:6:0.005, the raw materials are weighed according to the proportion, the raw materials are evenly mixed and placed into a corundum crucible, presintering is carried out for 5 hours at 400 ℃, grinding is carried out again after cooling, the raw materials are placed into the crucible, then the crucible is placed into a high-temperature furnace, roasting is carried out for 10 hours at 1150 ℃ in the air atmosphere, and the raw materials are naturally cooled to the room temperature, thus obtaining the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.99 (PO 4 ) 6 0.01Cr; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 3
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.99:6:0.005, weighing the raw materials according to the proportion, mixing uniformly, placing into a corundum crucible, presintering for 5 hours at 400 ℃, cooling, grinding again, placing into the crucible, placing into a high-temperature furnace, roasting for 10 hours at 1050 ℃ in nitrogen atmosphere, and naturally cooling to room temperature to obtainA near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.99 (PO 4 ) 6 0.01Cr; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 4
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.99:6:0.005, the raw materials are weighed according to the proportion, the raw materials are evenly mixed and placed into a corundum crucible, presintering is carried out for 5 hours at 400 ℃, grinding is carried out again after cooling, the raw materials are placed into the crucible, then the crucible is placed into a high-temperature furnace, roasting is carried out for 8 hours at 1050 ℃ in air atmosphere, and the raw materials are naturally cooled to room temperature, thus obtaining the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.99 (PO 4 ) 6 0.01Cr; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 5
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), (NH 4) 2HPO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.99:6:0.005, the raw materials are weighed according to the proportion, the raw materials are evenly mixed and placed into a corundum crucible, presintering is carried out for 5 hours at 400 ℃, grinding is carried out again after cooling, the raw materials are placed into the crucible, then the crucible is placed into a high-temperature furnace, roasting is carried out for 10 hours at 1050 ℃ in air atmosphere, and the raw materials are naturally cooled to room temperature, thus obtaining the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.99 (PO 4 ) 6 0.01Cr; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 6
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) SnO 2 (analytically pure) the molar ratio between them is 1:3.89:6:0.005:0.1, weighing the raw materials according to the proportion, placing the raw materials into a corundum crucible after uniformly mixing, presintering for 5 hours at 400 ℃, grinding the raw materials again after cooling, placing the raw materials into the crucible, placing the crucible into a high-temperature furnace, roasting the raw materials for 10 hours at 1050 ℃ in an air atmosphere, and naturally cooling the raw materials to room temperature to obtain the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.89 (PO 4 ) 6 0.01Cr,0.1Sn; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 7
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure), mgO (analytically pure), the molar ratio between them being 0.98:3.99:6:0.005:0.02, weighing the raw materials according to the proportion, placing the raw materials into a corundum crucible after uniformly mixing, presintering for 5 hours at 400 ℃, grinding the raw materials again after cooling, placing the raw materials into the crucible, placing the crucible into a high-temperature furnace, roasting the raw materials for 10 hours at 1050 ℃ in an air atmosphere, and naturally cooling the raw materials to room temperature to obtain the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of Ca 0.98 Ge 3.99 (PO 4 ) 6 0.01Cr,0.02Mg; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 8
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.99:6:0.005, weighing the raw materials according to the proportion, mixing uniformly, placing into a corundum crucible, presintering for 5 hours at 400 ℃, cooling, grinding again, placing into the crucible, and placing into a high-temperature furnaceRoasting for 10 hours at 1050 ℃ in air atmosphere, and naturally cooling to room temperature to obtain the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.99 (PO 4 ) 6 0.01Cr; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 9
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure), mgO (analytically pure), tiO 2 (analytically pure) the molar ratio between them is 0.99:3.98:6:0.005:0.01:0.01, the raw materials are weighed according to the proportion, the raw materials are evenly mixed and placed into a corundum crucible, presintering is carried out for 5 hours at 400 ℃, grinding is carried out again after cooling, the raw materials are placed into the crucible, then the crucible is placed into a high-temperature furnace, roasting is carried out for 10 hours at 1050 ℃ in air atmosphere, and natural cooling is carried out to room temperature, thus obtaining the near infrared luminescent powder. Obtaining white near infrared fluorescent powder with molecular formula of Ca 0.99 Ge 3.98 (PO 4 ) 6 0.01Cr,0.01Mg,0.01Ti; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 10
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.59:6:0.005, the raw materials are weighed according to the proportion, the raw materials are evenly mixed and placed into a corundum crucible, presintering is carried out for 5 hours at 400 ℃, grinding is carried out again after cooling, the crucible is placed into a crucible, then the crucible is placed into a high-temperature furnace, roasting is carried out for 10 hours at 1050 ℃ in air atmosphere, and natural cooling is carried out to room temperature, thus obtaining the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.59 (PO 4 ) 6 0.01Cr; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; fluorescent powder under 435nm blue light excitationThe maximum emission wavelength of (2) is around 747nm, and the luminescence is near infrared light.
Example 11
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.99:6:0.05, weighing the raw materials according to the proportion, placing the raw materials into a corundum crucible after uniformly mixing, presintering for 5 hours at 400 ℃, cooling, grinding again, placing into the crucible, placing into a high-temperature furnace, roasting for 10 hours at 1050 ℃ in the air atmosphere, and naturally cooling to room temperature to obtain the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.99 (PO 4 ) 6 0.05Cr; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue light excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light.
Example 12
The raw material is CaCO 3 (analytically pure), geO 2 (analytically pure), siO 2 (analytically pure), NH4H2PO4 (analytically pure), cr 2 O 3 (spectrally pure) with a molar ratio between them of 1:3.94:0.05:6:0.01, the raw materials are weighed according to the proportion, the raw materials are evenly mixed and placed into a corundum crucible, presintering is carried out for 5 hours at 400 ℃, grinding is carried out again after cooling, the raw materials are placed into the crucible, then the crucible is placed into a high-temperature furnace, roasting is carried out for 10 hours at 1050 ℃ in air atmosphere, and natural cooling is carried out to room temperature, thus obtaining the near infrared luminescent powder. The obtained near infrared fluorescent powder is white powder, and has molecular formula of CaGe 3.94 (PO 4 ) 6 0.01Cr,0.05Si; the excitation emission spectrums are all broadband emission, and the maximum excitation peak is about 435 nm; under 435nm blue excitation, the maximum emission wavelength of the fluorescent powder is near 747nm, and the luminescence is near infrared light, as shown in fig. 3.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The luminescent material as shown in figure 1,
Ca 1-x Ge 4-y-z (PO 4 ) 6 xM, yR, zCr formula 1;
in the formula 1, M is selected from one or more of Mg, sr, ba, zn;
r is selected from one or more of Sn, si, zr, ti;
0≤x≤1，0≤y≤4，0.0001≤z≤1。
2. the light-emitting material according to claim 1, wherein in formula 1, M is one or more selected from Mg, sr, zn;
r is selected from one or more of Sn, si and Ti;
0≤x≤0.5，0≤y≤1，0.0001≤z≤0.1。
3. luminescent material according to claim 1, characterized in that it is CaGe 3.99 (PO 4 ) 6 :0.01Cr、CaGe 4 (PO 4 ) 6 :0.01Cr、CaGe 3.59 (PO 4 ) 6 :0.01Cr、CaGe 3.99 (PO 4 ) 6 :0.05Cr、Ca 0.999 Ge 3.989 (PO 4 ) 6 :0.001Zn,0.001Sn,0.01Cr、Ca 0.98 Ge 3.99 (PO 4 ) 6 :0.01Cr,0.02Mg、Ca 0.99 Ge 3.98 (PO 4 ) 6 :0.01Cr,0.01Mg,0.01Ti、CaGe 3.89 (PO 4 ) 6 :0.01Cr,0.1Sn、CaGe 3.94 (PO 4 ) 6 One or more of 0.01Cr and 0.05 Si.
4. A method for producing a luminescent material, comprising: mixing a calcium source, a germanium source, a chromium source, a phosphorus source, an M source and an R source to obtain a mixture, and heating to obtain a luminescent material shown in a formula 1;
the M source and R source are optionally added;
Ca 1-x Ge 4-y-z (PO 4 ) 6 xM, yR, zCr formula 1;
in the formula 1, M is selected from one or more of Mg, sr, ba, zn;
r is selected from one or more of Sn, si, zr, ti;
0≤x≤1，0≤y≤4，0.0001≤z≤1。
5. the method of producing a light-emitting material according to claim 4, wherein the heating comprises: preheating the mixture at 400-500 ℃, cooling, and sintering the cooled mixture at 800-1500 ℃.
6. The method for producing a luminescent material according to claim 5, wherein the preheating time is 1 to 12 hours; the sintering time is 1-24 h.
7. The method of producing a luminescent material according to claim 4, wherein the molar ratio of the calcium source, the germanium source, the phosphorus source, the chromium source, the M source and the R source is (0.5-1.5): (3-5): (4-8): (0.001-0.1): (0-0.5).
8. The method of producing a luminescent material according to claim 4, wherein the chromium source includes one or more of nitrate, phosphate, oxide, chloride of chromium;
the calcium source comprises one or more of calcium oxide, carbonate and nitrate;
the germanium source comprises an oxide of germanium;
the phosphorus source comprises an ammonium phosphate salt.
9. The method of producing a light-emitting material according to claim 4, wherein the M source includes one or more of an oxide, a carbonate, and a nitrate of an M element;
the R source comprises one or more of oxide, carbonate and nitrate of R element.
Led light source, characterized by comprising a luminescent material according to any one of claims 1-3, or a luminescent material obtainable by a process for the preparation of a luminescent material according to any one of claims 4-9.
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