CN112552912A - Novel Cr3+Doped broadband near-infrared fluorescent powder, preparation and application - Google Patents
Novel Cr3+Doped broadband near-infrared fluorescent powder, preparation and application Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002223 garnet Substances 0.000 claims abstract description 16
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000005674 electromagnetic induction Effects 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000011651 chromium Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
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- 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
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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Abstract
The invention discloses a novel Cr3+A doped garnet structure near-infrared fluorescent powder and a preparation method of a near-infrared light source. The chemical general formula of the fluorescent powder is A3‑yCayB2‑x‑zCzD3O12:xCr3+,aRE2O3(0<x<0.5，1≤y<3，0<x + z is less than or equal to 2, z is more than 0 and less than 1.5, and a is more than or equal to 0 and less than or equal to 0.5); wherein A is one or the combination of more of Lu, Y, Gd, La and the like; b is one or a combination of more of Mg, Zn, Cu, Ni, Fe, Co, Ti and the like, C is one or a combination of more of Sc, In, Al, Ga and the like, and D is one or a combination of more of Ge, Si, Ti, Sn and the like; RE is one or a combination of more of Yb, Nd, Ce, Er and Pr; cr (chromium) component3+Are luminescent ions. The prepared fluorescent powder can be used for blue light and ultravioletThe light is effectively excited, and the packaged near-infrared light source has strong near-infrared broadband emission, so that the light source can be widely applied to the fields of plant illumination, food detection and the like.
Description
Technical Field
The invention relates to fluorescent powder applied to the field of luminescence, in particular to a near-infrared luminescent material converted from fluorescent powder and application thereof in the fields of plant illumination and food detection.
Background
With the continuous development of scientific technology and the continuous efforts of scientists, the near infrared technology has been widely applied to various fields such as security monitoring, unmanned driving, biomedical imaging, medical treatment and the like. At present, the common near-infrared light sources on the market mainly comprise incandescent lamps, halogen lamps, infrared light-emitting diodes and the like, however, all of them have inherent defects: incandescent and halogen lamps have the disadvantages of short life, large size, preheating before use, high energy consumption, low efficiency, etc. However, the infrared light emitting diode has a narrow emission band, a peak wavelength is shifted, and the light intensity is seriously reduced at a high temperature, so that the infrared light emitting diode cannot be widely applied to the near infrared technology.
In recent years, with the rapid development of white light LED technology, by means of the mature structure of its phosphor powder conversion white light LED (pc-LED), a blue light LED is used to excite a near-infrared phosphor powder to construct a phosphor conversion type LED light source, which becomes a new way to generate near-infrared light. The novel near-infrared light source prepared by the scheme of the blue light LED and the near-infrared fluorescent material has the advantages of low cost, wide and adjustable spectrum, high thermal stability, high power, energy conservation, environmental protection, mature structure, miniaturization, quick response and the like, and becomes the most effective way for solving the problem of lacking of miniaturization, quick response and broadband near-infrared light sources.
In recent years, Cr3+Because of having adjustable wavelength range, the doped boride, oxide and other materials show better near-infrared luminescence performance and show potential application prospect. In which Dinghao et al reported a Cr3+Doped ScBO3：Cr3+Boride near infrared fluorescent material [ Shao, Q., RSC Advances 2018,8(22), 12035-.]The material can be effectively excited by blue light, the center of an emission peak is about 800nm, and the material can be used as a near-infrared light source material. However, such phosphors are generally thermally stableThe overall performance of the near-infrared light source is greatly reduced due to low fixed bias, and further the commercial application of the near-infrared light source is limited. Based on the above, a novel near-infrared fluorescent powder is developed, and the fluorescent powder has important guiding significance for the production of related system products.
This patent discloses a novel unreported Cr3+The doped broadband near-infrared fluorescent powder has the advantages of wide and adjustable emission wavelength, excellent thermal stability, high luminous efficiency and the like, and is expected to solve the technical bottleneck of lacking a miniaturized, quick-response and broadband near-infrared light source.
Disclosure of Invention
The invention provides a novel garnet-structured broadband near-infrared fluorescent powder which can be effectively excited by blue light and ultraviolet light, and the preparation raw materials are easy to obtain, the process is simple, and the industrial production is easy to realize; the obtained near-infrared fluorescent powder has the advantages of wide half-peak width, high luminous efficiency and excellent thermal stability.
The novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder and the preparation method thereof have the following chemical compositions: a. the3-yCayB2-x-zCzD3O12:xCr3+,aRE2O3Wherein A is one or a combination of more of Lu, Y, Gd, La and the like; b is one or a combination of more of Mg, Zn, Cu, Ni, Fe, Co, Ti and the like; c is one or a combination of more of Sc, In, Al, Ga and the like; d is one or a combination of more of Ge, Si, Ti, Sn and the like; RE is one or a combination of Yb, Nd, Ce, Er and Pr.
The novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder is characterized in that 0<x<0.5，1≤y<3，0<x+z≤2，0≤z＜1.5，0≤a≤0.5。
The novel Cr3+The doped garnet-structured broadband near-infrared fluorescent powder is characterized by simultaneously containing Ca and Si elements.
The novel Cr3+The doped garnet-structured broadband near-infrared fluorescent powder is characterized in that the raw materials containing A, Ca, B, C and D are oxides or nitrates or carbonates corresponding to the elements.
The invention also provides the Cr3+The preparation method of the doped garnet structure broadband near-infrared fluorescent powder adopts a high-temperature solid-phase sintering method for preparation, and comprises the following specific steps:
(a) according to the formula A3-yCayB2-x-zCzD3O12:xCr3+Weighing oxides or nitrates containing A, Ca, B, C and D according to stoichiometric ratio, fully mixing, adding a certain amount of fluxing agent, grinding uniformly and sieving;
(b) putting the mixture obtained in the step (a) into a corundum crucible or a graphite crucible, moving the corundum crucible or the graphite crucible into a resistance furnace, sintering at a certain temperature, preserving heat for a period of time, and then cooling to room temperature along with the furnace;
(c) fully grinding, washing, drying and sieving the sintered product obtained in the step (b) to obtain novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
The Cr of the invention3+The preparation method of the doped garnet-structure broadband near-infrared fluorescent powder also comprises the following preferred scheme:
preferably, the specific fluxing agent in step (a) is B2O3、Li2CO3、CaF2、P2O5、LiF、NH4F、K2CO3Combinations of the raw materials; the content of the fluorescent material is 0-10 wt% of the total mass of the fluorescent material.
Preferably, in step (b), the number of times of firing in air may be one or more.
Preferably, in the step (b), the heating rate is 3-10 ℃/min, the roasting temperature is 1300-1500 ℃, and the single roasting time is 3-8 h.
Preferably, in the step (c), the roasted product is crushed, fully ground, washed with absolute ethyl alcohol for 2 to 5 times, filtered and dried.
The novel Cr3+The application method of the doped garnet structure broadband near-infrared fluorescent powder is characterized by comprising the following steps: the near-infrared phosphor of any one of claims 1 to 7 is applied to a near-infrared LED light source.
The novel Cr3+The garnet-structure-doped broadband near-infrared fluorescent powder is characterized in that the obtained novel garnet-structure broadband near-infrared fluorescent powder has broadband near-infrared luminescence under the excitation of 450nm light; the fluorescent powder and the silica gel are mixed to obtain slurry, the slurry is coated on an LED chip and cured to obtain a near-infrared LED light source, the emission peak is 650-1250 nm, the half-peak width is 100-300 nm, the internal quantum efficiency is 45-88%, the luminous intensity of the fluorescent powder is kept more than 70% of the room temperature at 473K, and the fluorescent powder can be widely applied to the fields of plant illumination, food detection and the like.
In conclusion, compared with the prior art, the method has the beneficial effects that:
(1) the fluorescent powder has larger composition selection and adjustment scope and good thermal stability.
(2) The fluorescent powder has a wider excitation range and has the strongest excitation peak around 450nm, so the fluorescent powder is very suitable for excitation of a blue light LED.
(3) The method for manufacturing the fluorescent powder is feasible, simple in production flow and convenient for large-scale production.
(4) The LED light source can realize the near infrared emission of a broadband (the half-peak width is 100-300 nm), high efficiency (the internal quantum efficiency is 45-88%) and high thermal stability (the luminous intensity of the fluorescent powder is kept more than 70% of the room temperature at 473K).
Drawings
FIG. 1 shows Cr3+Doping the excitation spectrum of the broadband near-infrared fluorescent powder.
FIG. 2 shows Cr3+The emission spectrum of the doped broadband near-infrared fluorescent powder.
FIG. 3 shows Cr3+And the emission spectrum of the rare earth doped broadband near-infrared fluorescent powder.
Detailed description of the preferred embodiments
Embodiment 1
Novel Cr3+The garnet-structure-doped broadband near-infrared fluorescent powder is solid powder and has the molecular formula of Lu2CaMg1.95Si3O12:0.05Cr3+. The preparation method comprises the following steps:
(1) weighing Lu according to stoichiometric ratio2O3：2.6533g，CaCO3：0.6673g，MgCO3：1.0960g，SiO2：1.2018g，Cr2O3: 0.0253 g. Mixing the above materials, adding flux B2O3、CaF2And LiF 0.0194g each, ground uniformly and sieved.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1350 ℃ at the heating rate of 5 ℃/min, preserving heat for 5h, and then cooling to room temperature along with the furnace;
(3) fully grinding the sintered product obtained in the step (2), washing the sintered product for 3 times by absolute ethyl alcohol, drying and sieving to obtain the novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
The near-infrared fluorescent powder obtained in the embodiment and a blue light LED chip are packaged and a fluorescence spectrum is tested, and the result shows that the emission peak of the obtained fluorescent powder is between 650 and 1000nm, and the half-peak width is 120 nm.
Embodiment 2
Novel Cr3+The garnet-structure-doped broadband near-infrared fluorescent powder is solid powder and has the molecular formula of Lu1.8Ca1.2Mg1.82Al0.1Ge3O12:0.08Cr3+. The preparation method comprises the following steps:
(1) weighing Lu (NO) according to stoichiometric ratio3)3·H2O：1.7055g，CaCO3：0.6005g，MgO：0.3668g，GeO2：1.5695g，Al(NO3)3·9H2O：0.1876g，Cr(NO3)3·9H2O: 0.1601 g. Mixing the above materials, adding flux B2O3、K2CO3And LiCO30.0470g of each, grinding uniformly and sieving.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1400 ℃ at the heating rate of 5 ℃/min, preserving heat for 6 hours, and then cooling to room temperature along with the furnace;
(3) fully grinding the sintered product obtained in the step (2), washing with absolute ethyl alcohol for 4 times, drying and sieving to obtain the novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
The near-infrared phosphor powder obtained in the embodiment and the blue light LED chip are packaged and the fluorescence spectrum is tested, and the result shows that the emission peak of the obtained phosphor powder is between 700 and 1100nm, and the half-peak width is 160 nm.
Embodiment 3
Novel Cr3+The garnet-structure-doped broadband near-infrared fluorescent powder is solid powder and has the molecular formula of Lu1.4Y0.4Ca1.2Mg1.35Ga0.5Si2GeO12:0.15Cr3+. The preparation method comprises the following steps:
(1) weighing Lu according to stoichiometric ratio2O3：1.3930g，Y2O3：0.2258g，CaCO3：0.6005g，MgCO3：0.5691g，SiO2：0.6009g，Ga2O3：0.2418，Cr2O3: 0.057 g. Fully mixing the raw materials, adding a fluxing agent LiF: 0.0286g and Li2CO3: 0.0257g, grinding uniformly and sieving.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1375 ℃ at the heating rate of 6 ℃/min, preserving heat for 4 hours, and then cooling to room temperature along with the furnace;
(3) fully grinding the sintered product obtained in the step (2), washing the sintered product for 3 times by absolute ethyl alcohol, drying and sieving to obtain the novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
The near-infrared fluorescent powder obtained in the embodiment and a blue light LED chip are packaged and a fluorescence spectrum is tested, and the result shows that the emission peak of the obtained fluorescent powder is between 650 and 1000nm, and the half-peak width is 115 nm.
Embodiment 4
Novel Cr3+The garnet-structure-doped broadband near-infrared fluorescent powder is solid powder and has the molecular formula of Lu1.5La0.5CaMg1.2Ga0.5Si3O12:0.3Cr3+. The preparation method comprises the following steps:
(1) weighing Lu according to stoichiometric ratio2O3：1.4925g，La2O3：0.4073g，CaCO3：0.5005g，MgCO3：0.5058g，SiO2：0.9013g，Cr2O3: 0.1140 g. Mixing the above materials, adding flux B2O3: 0.0800g and NH4F: 0.0800g, grinding uniformly and sieving.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1350 ℃ at a heating rate of 7 ℃/min, preserving heat for 5h, and then cooling to room temperature along with the furnace;
(3) fully grinding the sintered product obtained in the step (2), washing with absolute ethyl alcohol for 4 times, drying and sieving to obtain the novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
The near-infrared fluorescent powder obtained in the embodiment and a blue light LED chip are packaged and a fluorescence spectrum is tested, and the result shows that the emission peak of the obtained fluorescent powder is between 650 and 1100nm, and the half-peak width is 155 nm.
Embodiment 5
Novel Cr3+The garnet-structure-doped broadband near-infrared fluorescent powder is solid powder and has the molecular formula of Lu1.5Y0.5CaMg1.2Ga0.5Si3O12:0.3Cr3+,0.2Yb2O3. The preparation method comprises the following steps:
(1) weighing Lu (NO) according to stoichiometric ratio3)3·H2O：1.4925g，CaCO3：0.5005g，MgCO3：0.5059g，SiO2：0.9014g，Ga2O3：0.2418g，Cr2O3: 0.1140 g. Mixing the above materials, adding flux B2O3And Li2CO30.0212g each, grind evenly, sieve.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1375 ℃ at the heating rate of 5 ℃/min, preserving heat for 7 hours, and then cooling to room temperature along with the furnace;
(3) fully grinding the sintered product obtained in the step (2), washing with absolute ethyl alcohol for 4 times, drying and sieving to obtain the novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
The near-infrared fluorescent powder obtained in the embodiment and a blue light LED chip are packaged and a fluorescence spectrum is tested, and the result shows that the emission peak of the obtained fluorescent powder is between 650 and 1200nm, and the half-peak width is 185 nm.
Embodiment 6
Novel Cr3+The garnet-structure-doped broadband near-infrared fluorescent powder is solid powder and has the molecular formula of Lu2CaMg0.4Al1.3Si3O12:0.3Cr3+,0.2Nd2O3. The preparation method comprises the following steps:
(1) weighing Lu according to stoichiometric ratio2O3：1.9900g，CaCO3：0.5005g，MgCO3：0.1686g，SiO2：0.9014g，Al(NO3)3·9H2O：2.4383g，Nd2O3：0.1682g，Cr2O3: 0.1140 g. Mixing the above materials, adding CaF as fluxing agent2、B2O3And Li2CO30.0099g each, grind evenly and screen.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1350 ℃ at the heating rate of 8 ℃/min, preserving heat for 7.5h, and then cooling to room temperature along with the furnace;
(3) fully grinding the sintered product obtained in the step (2), washing the sintered product for 3 times by absolute ethyl alcohol, drying and sieving to obtain the novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
The near-infrared fluorescent powder obtained in the embodiment and a blue light LED chip are packaged and a fluorescence spectrum is tested, and the result shows that the emission peak of the obtained fluorescent powder is between 650 and 1000nm, and the half-peak width is 125 nm.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. Novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder and the preparation method thereof are characterized in that the fluorescent powder comprises the following chemical compositions: a. the3-yCayB2-x-zCzD3O12:xCr3+,aRE2O3Wherein A is one or a combination of more of Lu, Y, Gd, La and the like; b is one or a combination of more of Mg, Zn, Cu, Ni, Fe, Co, Ti and the like; c is one or a combination of more of Sc, In, Al, Ga and the like; d is one or a combination of more of Ge, Si, Ti, Sn and the like; RE is one or a combination of Yb, Nd, Ce, Er and Pr.
2. The novel garnet-structured broadband near-infrared phosphor as set forth in claim 1, wherein x is 0< x <0.5, y is 1. ltoreq. y <3, x + z is 0< x + z.ltoreq.2, z is 0. ltoreq. z < 1.5, and a is 0. ltoreq. a.ltoreq.0.5.
3. The novel garnet-structured broadband near-infrared phosphor is prepared by a high-temperature solid-phase sintering method, and comprises the following specific steps:
(a) according to the formula A3-yCayB2-x-zCzD3O12:xCr3+Weighing raw materials according to a stoichiometric ratio, fully mixing the raw materials containing A, Ca, B, C and D, adding a certain amount of fluxing agent, grinding uniformly and sieving;
(b) putting the mixture obtained in the step (a) into a corundum crucible or a graphite crucible, moving the corundum crucible or the graphite crucible into a resistance furnace, sintering at a certain temperature, preserving heat for a period of time, and then cooling to room temperature along with the furnace;
(c) charging the sintered product obtained in step (b)Separately grinding, washing, drying and sieving to obtain the novel Cr3+The doped garnet structure broadband near-infrared fluorescent powder.
4. Novel Cr according to claim 33+The preparation method of the doped garnet-structure broadband near-infrared fluorescent powder is characterized in that the raw materials containing A, Ca, B, C and D are oxides, nitrates or carbonates corresponding to all elements.
5. Novel Cr according to claim 33+The preparation method of the doped garnet-structured broadband near-infrared fluorescent powder is characterized in that the specific fluxing agent is B2O3、Li2CO3、Na2CO3、P2O5、K2CO3Combinations of the raw materials; the content of the fluorescent material is 0-10 wt% of the total mass of the fluorescent material.
6. Novel Cr according to claim 33+The preparation method of the doped garnet-structured broadband near-infrared fluorescent powder is characterized in that the sintering temperature is 1200-1600 ℃, and the heat preservation time is 1-10 h.
7. Novel Cr according to claim 33+The preparation method of the doped garnet structure broadband near-infrared fluorescent powder is characterized in that the heating rate of an electric furnace is 1-20 ℃/min, the heating mode is resistance furnace heating or electromagnetic induction furnace heating, and the heating atmosphere is air atmosphere.
8. Novel Cr3+The application method of the doped garnet structure broadband near-infrared fluorescent powder is characterized by comprising the following steps: the near-infrared phosphor of any one of claims 1 to 7 is applied to a near-infrared LED light source.
9. A novel preparation method of a near-infrared light source is characterized by comprising the following steps: and mixing the near-infrared fluorescent powder and silica gel to obtain slurry, coating the slurry on an LED chip, and curing to obtain the near-infrared LED light source.
10. Cr according to claims 1 to 93+The preparation method of the novel garnet-structure-doped broadband near-infrared fluorescent powder and the near-infrared light source is characterized in that the obtained novel garnet-structure-doped broadband near-infrared fluorescent powder has broadband near-infrared luminescence under the excitation of 450nm light; the near-infrared light source is prepared by packaging the fluorescent powder and a 450nm blue light LED, the emission peak is 650-1250 nm, the half-peak width is 100-300 nm, the internal quantum efficiency is 45-88%, and the luminous intensity at 473K is kept above 70% of the room temperature.
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