CN113308247A - Novel chromium-doped near-infrared diborate fluorescent powder and light source prepared from same - Google Patents
Novel chromium-doped near-infrared diborate fluorescent powder and light source prepared from same Download PDFInfo
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- CN113308247A CN113308247A CN202110576681.6A CN202110576681A CN113308247A CN 113308247 A CN113308247 A CN 113308247A CN 202110576681 A CN202110576681 A CN 202110576681A CN 113308247 A CN113308247 A CN 113308247A
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- 239000000843 powder Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium 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
- 238000002360 preparation method Methods 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 239000010431 corundum Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 238000000295 emission spectrum Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 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
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000005674 electromagnetic induction Effects 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 5
- 235000013305 food Nutrition 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 1
- 239000011651 chromium Substances 0.000 abstract 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 230000004044 response Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 235000013399 edible fruits Nutrition 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
- 239000002223 garnet Substances 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 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
- 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/778—Borates
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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
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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
- C09K11/7712—Borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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Abstract
The invention discloses a novel Cr3+A method for preparing near-infrared fluorescent powder with a doped bisborate structure and a near-infrared light source. The chemical general formula of the fluorescent powder is Y1‑x‑bMx(NyAlz)3‑a(BO3)4:aCr3+,bRE(0<x<1，0≤y<1，0≤z＜1，y+z＝1，0<a is less than or equal to 0.5, and b is less than 0.2 and more than or equal to 0); wherein M is Li+、K+、Na+One or a combination of a plurality of the components; n is one or a combination of more of Lu, Ga, Gd, Sc, In and the like; RE is Yb3+、Nd3+、Dy3+、Er3+、Pr3+One or a combination of more of the above; cr (chromium) component3+Are luminescent ions. The prepared fluorescent powder can be effectively excited by blue light or ultraviolet light, and the near red obtained after encapsulationThe external light source has strong broadband near-infrared emission, so that the device 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
The near infrared spectrum technology has the advantages of being rapid and nondestructive in detection and the like, and is widely applied to multiple fields of military affairs, food detection, medical treatment, face recognition, security monitoring, unmanned driving, agriculture and the like. Recently, researchers have proposed integrated, miniaturized, and efficient near-infrared light sources to detect freshness and safety of meat, fruits, and vegetables. The light source has the advantages of small volume, energy conservation, quick response, high efficiency and the like, and is expected to become a promising light source applied to smart phones. At present, the common near-infrared light sources on the market mainly include incandescent lamps, halogen lamps, infrared light emitting diodes and the like. However, the (al, ga) as-based near-infrared light emitting diode has a narrow half-peak width and cannot emit a wide near-infrared band; incandescent lamps and halogen lamps have the disadvantages of short service life, large volume, slow response, high energy consumption, low efficiency and the like, and the wide application of the incandescent lamps and the halogen lamps in the near infrared field is limited.
With the rapid development of white light LED technology, by taking the mature technology as a reference, a blue light LED is adopted to excite a near-infrared fluorescent material to construct a fluorescence conversion type LED (pc-LED) light source, and the method becomes a new approach for generating near-infrared light. The novel near-infrared light source prepared based on the compounding of the blue light LED and the near-infrared fluorescent material has the advantages of low cost, wide and adjustable spectrum, mature structure, high power, energy conservation, environmental protection and the like, and becomes the most effective way for solving the problem of lacking of a miniaturized and quick-response broadband near-infrared light source.
In recent years, Cr3+Activated fluorescenceThe powder shows strong broadband absorption in the range of 380-480 nm and has the characteristic of wider and adjustable wavelength in a near infrared region due to the unique electronic configuration of the luminous central ions, so that the powder shows potential application prospects in the technical field of near infrared spectroscopy. Among them, Zishan Sun et al reported a Cr3+Doped InBO3：Cr3+Oxide near infrared fluorescent material [ Sun Zishan. ceramics International,2021,47(10PA)]The material can be effectively excited by blue light, and the center of an emission peak is about 820nm, so that the material is expected to be used as a near-infrared light source material. However, the thermal stability of the borate fluorescent powder is generally low, which causes the comprehensive performance of the near infrared light source to be greatly reduced, and further causes the commercial application of the borate fluorescent powder to be limited. Based on the above, the near-infrared fluorescent powder with excellent thermal stability, wider half-peak width of emission peak and high luminous efficiency is developed, and has important guiding significance for the production of related system products.
This patent discloses a novel unreported Cr3+The double borate substrate doped broadband near-infrared fluorescent powder and the light source prepared from the same have the advantages of wider and adjustable emission wavelength, excellent thermal stability, high luminous efficiency and the like, and are expected to solve the technical bottleneck of lacking miniaturization, quick response and broadband near-infrared light sources.
Disclosure of Invention
The invention provides a novel ultraviolet or blue light excited broad-band near-infrared fluorescent powder with a bisborate structure, which has the advantages of easily obtained preparation raw materials, simple process and easy industrial production; 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 wide-band near-infrared fluorescent powder with a doped bisborate structure and the preparation method thereof comprise the following chemical compositions: y is1-x-bMx(NyAlz)3-a(BO3)4:aCr3+bRE, wherein M is Li+、K+、Na+One or a combination of a plurality of the components; n is one or a combination of more of Lu, Ga, Gd, Sc, In and the like; RE is Yb3+、Nd3+、Dy3+、Er3+、Pr3+One or a combination of several of them.
The novel Cr3+The wide-band near-infrared fluorescent powder with a doped bisborate structure is characterized in that 0<x<1，0≤y<1，0≤z＜1，y+z＝1，0<a≤0.5，0≤b＜0.2。
The novel Cr3+The wide-band near-infrared fluorescent powder with a doped bisborate structure is characterized in that the fluorescent powder simultaneously contains Li+、K+、Na+One or more elements of (a).
The novel Cr3+The wide-band near-infrared fluorescent powder with doped double borate structure is characterized by containing Y, M, N, Al, B and Cr3+And the raw material of RE is oxide or nitrate or carbonate or hydroxide corresponding to each element.
The invention also provides the Cr3+The preparation method of the broad-band near-infrared fluorescent powder with the doped bisborate structure adopts a high-temperature solid-phase sintering method for preparation, and comprises the following specific steps:
(a) according to the formula Y1-x-bMx(NyAlz)3-a(BO3)4:aCr3+bRE weighing Y, M, N, Al, B and Cr in stoichiometric ratio3+Fully mixing oxide or nitrate or carbonate or hydroxide of RE element, adding a certain amount of fluxing agent, grinding uniformly, and sieving;
(b) loading the mixture obtained in the step (a) into a corundum crucible or a graphite crucible, then moving the corundum crucible or the graphite crucible into a muffle furnace, sintering the mixture at a certain temperature, preserving heat for a period of time, and then cooling the mixture to room temperature along with the furnace;
(c) grinding, washing, drying and sieving the sintered product obtained in the step (b) to obtain novel Cr3+The wide band near infrared fluorescent powder with a doped bisborate structure.
The Cr of the invention3+The preparation method of the broad-band near-infrared fluorescent powder with the doped bisborate structure also comprises the following preferred scheme:
preferably, the specific fluxing agent in step (a) is CaF2、P2O5、NH4F, and the like; 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 temperature rise rate is 3-10 ℃/min, the roasting temperature is 800-.
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 broad band near-infrared fluorescent powder with the doped bisborate structure is characterized in that: 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 novel broad-band near-infrared fluorescent powder with the double borate structure is characterized in that the obtained broad-band near-infrared fluorescent powder with the double borate structure has broad-band near-infrared luminescence under the excitation of ultraviolet or blue light; the fluorescent powder and the silica gel are mixed to obtain slurry, the slurry is coated on a 400-450 nm 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 50-95%, the luminous intensity of the fluorescent powder is kept above 80% 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 420nm, 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 near-infrared emission with a wide band (the half-peak width is 100-300 nm), high efficiency (the internal quantum efficiency is 50-95%) and high thermal stability (the luminous intensity of the fluorescent powder is kept more than 80% 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 wide-band near-infrared fluorescent powder with a doped bisborate structure is made of solid powder and has a molecular formula of Y0.99Li0.01Ga2.97(BO3)4:0.03Cr3+. The preparation method comprises the following steps:
(1) weighing Y according to stoichiometric ratio2O3：0.4201g，Li2CO3：0.0013g，Ga2O3：1.0463g，B2O3：0.5234g，Cr2O3: 0.0085 g. Mixing the above materials, adding CaF as fluxing agent2And P2O50.1g of each, grinding uniformly and sieving.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min, preserving heat for 5 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 wide band near infrared fluorescent powder with a doped bisborate structure.
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 140 nm.
Embodiment 2
Novel Cr3+The wide-band near-infrared fluorescent powder with a doped bisborate structure is made of solid powder and has a molecular formula of Y0.99Li0.01Ga1.44Al1.5(BO3)4:0.06Cr3+. The preparation method comprises the following steps:
(1) weighing Y according to stoichiometric ratio2O3：0.2067g，Li2CO3：0.0006g，Al(NO3)3·9H2O:1.0409g，Ga2O3：0.2496g，H3BO3：0.4575g，Cr(NO3)3·9H2O: 0.0444 g. Mixing the above materials, adding CaF as fluxing agent2And NH4F, 0.02g each, grinding uniformly and sieving.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1200 ℃ at a 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 located between 700-1100nm, and the half-peak width is 150 nm.
Embodiment 3
Novel Cr3+The wide-band near-infrared fluorescent powder with a doped bisborate structure is made of solid powder and has a molecular formula of Y0.99Na0.01In2.94(BO3)4:0.06Cr3+. The preparation method comprises the following steps:
(1) weighing Y according to stoichiometric ratio2O3：0.3366g，NaNO3：0.0012g，In2O3：1.2290g，B2O3：0.4193g，Cr2O3: 0.0137 g. Mixing the above materials, adding flux P2O5: 0.0286g and NH4F: 0.05g, grinding uniformly and sieving.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1200 ℃ at a 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 wide band near infrared fluorescent powder with a doped bisborate structure.
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 located between 650 and 1100nm, and the half-peak width is 180 nm.
Embodiment 4
Novel Cr3+The wide-band near-infrared fluorescent powder with a doped bisborate structure is made of solid powder and has a molecular formula of Y0.99Li0.01Ga1.92Sc0.5Al0.5(BO3)4：0.08Cr3+. The preparation method comprises the following steps:
(1) weighing Y according to stoichiometric ratio2O3：0.2876g，Li2O：0.0003g，Ga2O3：0.4630g，Sc2O3：0.0887g，Al(NO3)3·9H2O：0.4826g，H3BO3：0.6364g，Cr(NO3)3·9H2O: 0.0411 g. Mixing the above raw materials, adding flux NH4F and CaF20.0400g each, grind evenly, sieve.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1250 ℃ at the heating rate of 7 ℃/min, preserving heat for 5 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 wide band near infrared fluorescent powder with a doped bisborate structure.
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+Broad-band near-infrared fluorescence of doped bisborate structureThe light powder is solid powder with molecular formula of Y0.79Li0.01Ga1.42Sc0.5Al(BO3)4：0.08Cr3+,0.2Yb3+. The preparation method comprises the following steps:
(1) weighing Y according to stoichiometric ratio2O3：0.2736g，Li2CO3：0.0011g，Ga2O3：0.4082g，Sc2O3：0.1057g，Al2O3：0.3129g，H3BO3：0.7587g，Yb2O3：0.1208g，Cr2O3: 0.0.0186 g. Mixing the above materials, adding CaF as fluxing agent2、P2O5And NH4F, 0.015g each, grinding evenly and sieving.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1100 ℃ at a 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 wide band near infrared fluorescent powder with a doped bisborate structure.
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 wide-band near-infrared fluorescent powder with a doped bisborate structure is made of solid powder and has a molecular formula of Y0.79Na0.01Ga1.9In0.2Al0.8(BO3)4：0.1Cr3+,0.2Nd3+. The preparation method comprises the following steps:
(1) weighing Y according to stoichiometric ratio2O3：0.1944g，Na2CO3：0.0003g，Ga2O3：0.3881g，In(NO3)3：0.0605g，Al(NO3)3·9H2O：0.6542g，H3BO3：0.5391g，Nd2O3：0.1466g，Cr2O3: 0.0165 g. Mixing the above materials, adding flux P2O5And NH4F0.012 g each, grind evenly, sieve.
(2) Loading the mixture into a corundum crucible, transferring into a resistance furnace, heating to 1250 ℃ at the heating rate of 8 ℃/min, preserving heat for 7.5 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 wide band near infrared fluorescent powder with a doped bisborate structure.
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 wide-band near-infrared fluorescent powder with the doped bisborate structure and the preparation method thereof are characterized in that the chemical composition of the fluorescent powder is as follows: y is1-x-bMx(NyAlz)3-a(BO3)4:aCr3+bRE, wherein M is Li+、K+、Na+One or a combination of a plurality of the components; n is one or a combination of more of Lu, Ga, Gd, Sc, In and the like; RE is Yb3+、Nd3+、Dy3+、Er3+、Pr3+One or a combination of several of them.
2. The novel double borate structured broadband near infrared phosphor as claimed in claim 1, wherein 0< x <1, 0< y <1, 0< z <1, y + z ═ 1, 0< a < 0.5, 0< b < 0.2.
3. The novel broad-band near-infrared fluorescent powder with the diborate structure as claimed in claim 1 is prepared by a high-temperature solid-phase sintering method, and comprises the following specific steps:
(a) according to the formula Y1-x-bMx(NyAlz)3-a(BO3)4:aCr3+bRE weighing Y, M, N, Al, B and Cr in stoichiometric ratio3+Fully mixing the raw materials of RE, adding a certain amount of fluxing agent, grinding uniformly, and sieving;
(b) loading the mixture obtained in the step (a) into a corundum crucible or a graphite crucible, then moving the corundum crucible or the graphite crucible into a muffle furnace, sintering the mixture at a certain temperature, preserving heat for a period of time, and then cooling the mixture to room temperature along with the furnace;
(c) grinding, washing, drying and sieving the sintered product obtained in the step (b) to obtain novel Cr3+The wide band near infrared fluorescent powder with a doped bisborate structure.
4. Novel Cr according to claim 33+The preparation method of the wide-band near-infrared fluorescent powder with the doped bisborate structure is characterized by comprising Y, M, N, Al, B and Cr3+And the raw material of RE is oxide or nitrate or carbonate or hydroxide corresponding to each element.
5. Novel Cr according to claim 33+The preparation method of the broad-band near-infrared fluorescent powder with the doped bisborate structure is characterized in that the specific fluxing agent is CaF2、P2O5、NH4F, and the like; 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+Doped bisborate structuresThe preparation method of the broadband near-infrared fluorescent powder is characterized in that the sintering temperature is 800-1300 ℃, and the heat preservation time is 1-10 h.
7. Novel Cr according to claim 33+The preparation method of the wide-band near-infrared fluorescent powder with the doped bisborate structure is characterized in that the heating rate of an electric furnace is 1-20 ℃/min, the heating mode is muffle furnace heating or electromagnetic induction furnace heating, and the heating atmosphere is air atmosphere.
8. Novel Cr3+The application method of the broad band near-infrared fluorescent powder with the doped bisborate structure is characterized in that: 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 ultraviolet or blue light 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 broad-band near-infrared fluorescent powder doped with the bisborate structure and the near-infrared light source is characterized in that the obtained novel broad-band near-infrared fluorescent powder with the bisborate structure has broad-band near-infrared luminescence under the excitation of ultraviolet or blue light; the fluorescent powder and the LED chip with the wavelength of 400-450 nm are packaged to prepare the near-infrared light source, the emission spectrum of the near-infrared light source is 650-1250 nm, the half-peak width of the near-infrared light source is 100-300 nm, the internal quantum efficiency of the near-infrared light source is 50-95%, and the luminous intensity at 473K temperature is kept above 80% of the room temperature.
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