CN114806564B - Trivalent chromium ion doped fluoroantimonate near infrared fluorescent material, preparation method and LED light source thereof - Google Patents
Trivalent chromium ion doped fluoroantimonate near infrared fluorescent material, preparation method and LED light source thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 18
- 239000011651 chromium Substances 0.000 claims abstract description 89
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003333 near-infrared imaging Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 239000010937 tungsten Substances 0.000 description 2
- -1 tungsten halogen Chemical class 0.000 description 2
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 230000004297 night vision Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying 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
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/75—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth containing antimony
- C09K11/758—Vandates; Chromates; Molybdates; Tungstates
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- H—ELECTRICITY
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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 trivalent chromium ion doped fluoroantimonate near infrared fluorescent material and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving an Sb source and a Cr source in an HF solution, stirring until the Sb source and the Cr source are dissolved, adding a Na source, and continuously stirring to form a mixed solution; the mixed solution is put into reaction equipment for reaction, washed and dried to obtain Cr 3+ Doped fluoroantimonate near infrared fluorescent material; the Cr 3+ The chemical composition of the fluorine antimonate doped near infrared fluorescent material is as follows: naSbF 4 ：xCr 3+ X=0.5 to 5%. Cr provided by the invention 3+ The near infrared fluorescent material doped with the fluorine antimonate has high fluorescence quantum efficiency and absorption efficiency, and the preparation method is simple and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a trivalent chromium ion doped fluoroantimonate near infrared fluorescent material, a preparation method and an LED light source thereof.
Background
The near infrared spectrum technology has different scattering spectrum shapes and intensities for substances, and can be widely applied to the fields of biomedical imaging, food detection, night vision imaging and the like. Currently, commercial near infrared light sources are mainly tungsten halogen lamps, near infrared LEDs and infrared lasers. However, the traditional halogen tungsten has the defects of wide emission spectrum, large volume, slow response, low efficiency, short service life, large visible light content in the spectrum and the like. The near infrared LED and the infrared laser have the characteristics of small volume and high efficiency, but have narrow emission band, unstable emission wavelength and poor luminous thermal stability, and cannot be widely applied to the technical field of near infrared spectrums. With the rapid development of the LED technology, the near infrared light source can be realized by exciting the near infrared fluorescent powder by using the high-efficiency blue LED chip. The LED light source (pc-LED) based on fluorescent powder conversion has the advantages of wide emission spectrum, controllable adjustment, high thermal stability, high efficiency, low cost and the like, and has wide application prospect. At present, the broadband near-infrared pc-LED technology is in the primary stage, has low photoelectric conversion efficiency, small output power and insufficient emission band, cannot meet the wide application of near infrared, and is a key for solving the problems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a trivalent chromium ion (Cr 3+ ) The preparation method of the fluorine-doped antimonate near-infrared fluorescent material adopts a hydrothermal method, is simple to operate, has easily available raw materials and low cost, and is suitable for industrial mass production.
The invention also aims to provide a method for preparing trivalent chromium ions (Cr 3+ ) Near infrared fluorescent material doped with fluorine antimonate and Cr 3+ The fluorine antimonate doped near infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm, emits broadband near infrared light with the wavelength of 700-900nm, has the strongest wavelength of 760-770 nm, has the half-peak width of 110-120 nm and has the quantum efficiency of 53-55%.
The invention also aims to solve the technical problem of providing an LED light source, wherein the electro-optic conversion efficiency of the LED light source is 9-12% at 100mA, and the LED light source is a broadband near infrared LED light source.
In order to solve the technical problems, the invention provides a Cr 3+ The preparation method of the fluorine-doped antimonate near-infrared fluorescent material comprises the following steps:
dissolving an Sb source and a Cr source in an HF solution, stirring until the Sb source and the Cr source are dissolved, adding a Na source, and continuously stirring to form a mixed solution;
the mixed solution is put into reaction equipment for reaction, washed and dried to obtain Cr 3+ Doped fluoroantimonate near infrared fluorescent material;
the Cr 3+ The chemical composition of the fluorine antimonate doped near infrared fluorescent material is as follows: naSbF 4 ：xCr 3+ ，x＝0.5～5％。
Preferably, the ratio of the sum of the addition amounts of the Sb source, the Cr source and the Na source to the use amount of the HF solution is 0.7-0.9 g/mL.
Preferably, in the Sb source and the Na source, the molar ratio of Sb to Na is 1: (1-3);
in the Cr source and the Sb source, the molar ratio of Cr to Sb is (0.005-0.05): 1.
preferably, the Sb source is Sb 2 O 3 Or Sb (CH) 3 COO) 3 ；
The Cr source is Cr (NO) 3 ) 3 ·9H 2 O or Cr 2 O 3 ；
The Na source is NaF, naHF 2 And Na (Na) 2 CO 3 One of the following;
the mass fraction of the HF solution is 20-60wt%.
Preferably, the mixed solution is put into a high-pressure reaction kettle, reacted for 6-15 hours at 180-220 ℃, cooled, washed and dried to obtain the finished product.
Preferably, in the washing and drying process, deionized water is used for washing 1-3 times, and then an organic solvent is used for washing 1-2 times so as to remove the reaction liquid remained on the surface, and then drying is completed at the temperature of 50-100 ℃.
In order to solve the problems, the invention also provides a Cr 3+ The near infrared fluorescent material doped with the fluorine antimonate is prepared by the preparation method.
Preferably, the Cr 3+ The fluorine antimonate doped near infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm, emits broadband near infrared light with the wavelength of 700-900nm, has the strongest wavelength of 760-770 nm, has the half-peak width of 110-120 nm and has the quantum efficiency of 53-55%.
In order to solve the above problems, the present invention also provides an LED light source, which is manufactured by the following method: the Cr is treated by 3+ Uniformly mixing the fluorine antimonate doped near infrared luminescent fluorescent material with epoxy resin to obtain a mixed material;
and coating the mixed material on a blue light LED chip, and curing to obtain a finished product.
Preferably, the Cr 3+ The near infrared luminescent fluorescent material doped with fluorine antimonate and epoxy resin are mixed according to the following ratio of 1: mixing the components (1-4) in a mass ratio.
The implementation of the invention has the following beneficial effects:
cr provided by the invention 3+ The preparation method of the fluorine-doped antimonate near-infrared fluorescent material has the advantages of simple process, short period, low cost, high yield and easy mass production. Cr obtained by the preparation 3+ The fluorine antimonate doped near infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm, emits broadband near infrared light with the wavelength of 700-900nm, has the strongest wavelength of 760-770 nm, has the half-peak width of 110-120 nm and has the quantum efficiency of 53-55%. The Cr is treated with 3+ The fluorine antimonate doped near infrared fluorescent material is used for preparing an LED light source, the electro-optic conversion efficiency of the LED light source is 9-12% at 100mA, the LED light source is a broadband near infrared LED light source, and the LED light source has wide application prospect in the near infrared imaging field.
Drawings
FIG. 1 is a NaSbF obtained in example 1 of the present invention 4 :0.5％Cr 3+ XRD spectrum of near infrared fluorescent material;
FIG. 2 is a NaSbF obtained in example 1 of the present invention 4 :0.5％Cr 3+ Excitation and emission spectra of near infrared fluorescent materials;
FIG. 3 is a sample NaSbF prepared in example 4 of the present invention 4 :3％Cr 3+ A quantum efficiency map of the near infrared fluorescent material;
FIG. 4 is an electroluminescence spectrum of an LED light source prepared by using the near infrared fluorescent materials prepared in examples 1 to 5 as a raw material.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent.
In order to solve the technical problems, the invention provides a method for preparing trivalent chromium ions (Cr 3+ ) The preparation method of the fluorine-doped antimonate near infrared fluorescent material comprises the following steps:
s1, dissolving an Sb source and a Cr source in an HF solution, stirring until the Sb source and the Cr source are dissolved, adding a Na source, and continuously stirring to form a mixed solution;
s2, loading the mixed solution into reaction equipment for reaction, and washing and drying to obtain Cr 3+ Doped fluoroantimonate near infrared fluorescent material;
the Cr 3+ The chemical composition of the fluorine antimonate doped near infrared fluorescent material is as follows: naSbF 4 ：xCr 3+ ，x＝0.5～5％。
ABCF in the prior art 6: xCr 3+ Is more common Cr 3+ Doped near infrared fluorescent material, wherein A represents alkali metal, B represents alkaline earth metal, and C represents element of third main group or third subgroup. Most of the near infrared fluorescent materials belong to a double-calcium-titanium structure, B 2+ And C 3+ The ions adopt octahedral coordination, cr 3+ Ions tend to occupy both sites at the same time, so that the distance between the two luminescent centers is too short, causing fluorescence quenching.
The invention adopts the fluoroantimonate NaSbF 4 In the structure of (1), sb 3+ The ion coordinates with 6 fluoride ions to form distorted octahedron, the distance between the octahedrons is larger, na + The ion adopts nine coordination. Cr (Cr) 3+ The ions only occupy Sb 3+ Lattice site, large fluorescence quenching concentration, high fluorescence quantum efficiency, [ SbF ] 6 ]Serious distortion of octahedron can solve and forbidden Cr to a great extent 3+ And the forbidden transition of the d3 outer layer electron of the ion is selected to obtain larger fluorescence quantum efficiency and absorption efficiency.
In step S1, preferably, the ratio of the sum of the addition amounts of the Sb source, cr source and Na source to the amount of the HF solution is 0.7 to 0.9g/mL. It is noted that the ratio of the sum of the addition amounts of the Sb source, the Cr source and the Na source to the dosage of the HF solution is less than 0.7g/mL, and a hetero-phase appears to reduce the luminous efficiency of the sample; the ratio of the sum of the addition amounts of the Sb source, the Cr source and the Na source to the dosage of the HF solution is more than 0.9g/mL, so that the impurity phase appears, the luminous efficiency of a sample is reduced, and the crystallinity of the sample is reduced. More preferably, the ratio of the sum of the addition amounts of the Sb source, cr source and Na source to the amount of HF solution is 0.8g/mL.
Preferably, in the Sb source and the Na source, the molar ratio of Sb to Na is 1: (1-3), specifically, the molar ratio of Sb to Na is less than 1:1, the generation of a hetero-phase containing Sb element is caused; the molar ratio of Sb to Na is more than 1:3, will result in the generation of a Na element-containing impurity phase. More preferably, the molar ratio of Sb to Na is 1:1.
preferably, in the Cr source and the Sb source, the molar ratio of Cr to Sb is (0.005 to 0.05): 1, specifically, the molar ratio of Cr to Sb is less than 0.005:1 will result in NaSbF 4 :Cr 3+ The luminous efficiency of the fluorescent powder is very low; the molar ratio of Cr to Sb is more than 0.05:1 will result in NaSbF 4 :Cr 3+ Concentration quenching of the phosphor occurs and Na is generated 3 CrF 6 And (3) impurity phase. More preferably, the molar ratio of Cr to Sb is (0.01 to 0.03): 1.
preferably, the Sb source is Sb 2 O 3 Or Sb (CH) 3 COO) 3 The method comprises the steps of carrying out a first treatment on the surface of the The Cr source is Cr (NO) 3 ) 3 ·9H 2 O or Cr 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Na source is NaF, naHF 2 And Na (Na) 2 CO 3 One of the following; the mass fraction of the HF solution is 20-60wt%. More preferably, the Sb source is selected from Sb 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Cr source is Cr (NO) 3 ) 3 ·9H 2 O; the Na source is NaHF 2 . The mass fraction of the HF solution is 25-35 wt%.
In the step S2, compared with the near infrared fluorescent material prepared by adopting a coprecipitation method in the prior art, the near infrared fluorescent material prepared by adopting a hydrothermal method has the advantages of simple process, short period, low cost, high yield and easy mass production. In addition, the solvent is single in the preparation process, only HF solution is needed, impurities are not easy to generate, and the prepared finished product has pure crystalline phase.
Preferably, the mixed solution is put into a high-pressure reaction kettle, reacted for 6-15 hours at 180-220 ℃, cooled, washed and dried to obtain the finished product. More preferably, the reaction is carried out for 10 to 12 hours at the temperature of 200 to 220 ℃, then the product is cooled, washed and dried, and then the finished product is obtained.
It should be noted that technical difficulties exist in the post-treatment process in the preparation process. After the hydrothermal reaction is finished, naSb needs to be washed and removed 1-x F 4 :xCr 3+ The HF solution remained on the surface of the near infrared fluorescent material is directly added with an organic solvent for washing, so that the surface morphology of a product is easily influenced, the product tends to be fluffy, and the luminous efficiency is influenced. On the other hand, due to NaSbF 4 Is relatively high in solubility, and directly washing with a large amount of deionized water can lead to NaSbF 4 Dissolving and separating out CrF 3 . Thus, the composition of the wash solution employed in the wash process has a major impact on the final finished product properties. Preferably, in the washing and drying process, deionized water is firstly used for washing 1-3 times, then an organic solvent is used for washing 1-2 times, so that the reaction liquid remained on the surface is removed, and then the drying is finished at the temperature of 50-100 ℃. Preferably, the organic solvent is ethanol or acetone, and the drying is completed at the temperature of 70-80 ℃.
In conclusion, cr prepared by the preparation method 3+ The doped fluoroantimonate near infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm, emits broadband near infrared light with the wavelength of 700-900nm, has the strongest wavelength of 760-770 nm, has the half-peak width of 110-120 nm and has the quantum efficiency of 53-55%.
Correspondingly, the invention also provides an LED light source, which is prepared by the following method: the Cr is treated by 3+ Uniformly mixing the fluorine antimonate doped near infrared luminescent fluorescent material with epoxy resin to obtain a mixed material; and coating the mixed material on a blue light LED chip, and curing to obtain a finished product. Preferably, the Cr 3+ The near infrared luminescent fluorescent material doped with fluorine antimonate and epoxy resin are mixed according to the following ratio of 1: mixing the components (1-4) in a mass ratio. The electro-optic conversion efficiency of the LED light source is 9-12% at 100mA, and the LED light source is a broadband near-infrared LED light source and has wide application prospect in the near-infrared imaging field.
The invention is further illustrated by the following examples:
example 1
Cr (chromium) 3+ The preparation method of the fluorine antimonate doped near infrared fluorescent material comprises the following steps:
0.024g Cr (NO) 3 ) 3 ·9H 2 O，1.74g Sb 2 O 3 Dissolving in 3mL of 49wt% HF solution, stirring to dissolve completely, and adding 0.4199g of NaHF 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220deg.C for 10 hr, cooling to room temperature, centrifuging with deionized water for 2 times, centrifuging with absolute ethanol for 1 time, filtering, and oven drying at 70deg.C for 8 hr to obtain NaSbF 4 :0.5％Cr 3+ 。
Example 2
Cr (chromium) 3+ The preparation method of the fluorine antimonate doped near infrared fluorescent material comprises the following steps:
0.024g Cr (NO) 3 ) 3 ·9H 2 O，1.74g Sb 2 O 3 Dissolving in 3mL of 20wt% HF solution, stirring to dissolve completely, adding 0.4199g NaF, stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 200deg.C for 10h, cooling to room temperature, centrifuging with deionized water for 2 times, centrifuging with absolute ethanol for 1 time, filtering, and oven drying at 80deg.C for 8 hr to obtain NaSbF 4 :0.5％Cr 3+ 。
Example 3
Cr (chromium) 3+ The preparation method of the fluorine antimonate doped near infrared fluorescent material comprises the following steps:
0.048g Cr (NO) 3 ) 3 ·9H 2 O，1.731g Sb 2 O 3 Dissolving in 3mL of 30wt% HF solution, stirring to dissolve completely, and adding 0.6199g of NaHF 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220deg.C for 10 hr, cooling to room temperature, centrifuging with deionized water for 2 times, centrifuging with absolute ethanol for 1 time, filtering, and oven drying at 70deg.C for 8 hr to obtain NaSbF 4 :1％Cr 3+ 。
Example 4
The method comprises the following steps ofCr 3+ The preparation method of the fluorine antimonate doped near infrared fluorescent material comprises the following steps:
0.144g of Cr (NO) 3 ) 3 ·9H 2 O，1.696g Sb 2 O 3 Dissolving in 3mL of 49wt% HF solution, stirring to dissolve completely, and adding 0.6199g of NaHF 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220deg.C for 10 hr, cooling to room temperature, centrifuging with deionized water for 2 times, centrifuging with absolute ethanol for 1 time, filtering, and oven drying at 70deg.C for 8 hr to obtain NaSbF 4 :3％Cr 3+ 。
Example 5
Cr (chromium) 3+ The preparation method of the fluorine antimonate doped near infrared fluorescent material comprises the following steps:
0.24g of Cr (NO) 3 ) 3 ·9H 2 O，1.661g Sb 2 O 3 Dissolving in 3mL of 49wt% HF aqueous solution, stirring to dissolve completely, and adding 0.6199g of NaHF 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220 deg.C for 10 hr, cooling to room temperature, centrifuging with deionized water for 2 times, centrifuging with absolute ethanol for 1 time, filtering, and oven drying at 70 deg.C for 8 hr to obtain NaSbF 4 :5％Cr 3+ 。
For Cr prepared in example 1 3+ XRD test and excitation and emission spectrum evaluation of near infrared fluorescent materials doped with fluoroantimonate, FIG. 1 is a schematic diagram of Cr obtained in example 1 3+ As can be seen from FIG. 1, XRD spectra of the near infrared fluorescent powder doped with fluorine antimonate show that the XRD diffraction peak of the prepared sample is consistent with that of the standard card JCPDS No.34-0428, indicating that the prepared NaSbF 4 :0.5％Cr 3+ Is pure phase.
FIG. 2 is a Cr produced in example 1 3+ The excitation spectrum of the sample consists of two broad peaks of 428nm and 600nm, wherein the strongest excitation is positioned at 428nm, the emission of broad peak near infrared light is 700-900nm, and the strongest emission wavelength is 762nm.
Meanwhile, for NaSbF prepared in example 4 4 :3％Cr 3+ Near infrared fluorescent material was tested, graph3 is a fluorescence quantum efficiency map thereof, and as can be seen from FIG. 3, naSbF 4 :3％Cr 3+ The fluorescence quantum efficiency of (2) was 54.5%.
The Cr produced in examples 1 to 5 was further treated 3+ The method for preparing the LED light source by doping the fluorine antimonate comprises the following steps:
0.2g of epoxy resin was mixed with 0.1g of Cr prepared in examples 1 to 5 3+ The near infrared fluorescent material doped with the fluorine antimonate is fully and uniformly mixed, coated on a blue light GaN chip, placed in a vacuum drying oven, dried for 30min at 60 ℃, then transferred to an oven, and dried for 4h at 120 ℃ to obtain the LED light source. Fig. 4 is an electroluminescence spectrum of the LED light source at a driving current of 100 mA. As can be seen from FIG. 4, the NaSbF obtained in example 4 is compared with examples 1 to 3 and example 5 4 :3％Cr 3+ The near infrared fluorescent material has better luminous intensity.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (10)
1. The preparation method of the trivalent chromium ion doped fluoroantimonate near infrared fluorescent material is characterized by comprising the following steps of:
dissolving an Sb source and a Cr source in an HF solution, stirring until the Sb source and the Cr source are dissolved, adding a Na source, and continuously stirring to form a mixed solution;
the mixed solution is put into reaction equipment for reaction, washed and dried to obtain Cr 3+ Doped fluoroantimonate near infrared fluorescent material;
the Cr 3+ The chemical composition of the fluorine antimonate doped near infrared fluorescent material is as follows: naSbF 4 ：xCr 3+ ，x＝0.5～5％。
2. The method for preparing a trivalent chromium ion doped fluoroantimonate near infrared fluorescent material according to claim 1, wherein the ratio of the sum of the addition amounts of the Sb source, the Cr source and the Na source to the dosage of the HF solution is 0.7-0.9 g/mL.
3. The method for preparing the trivalent chromium ion doped fluoroantimonate near infrared fluorescent material according to claim 1, wherein the molar ratio of Sb to Na in the Sb source to Na source is 1: (1-3);
in the Cr source and the Sb source, the molar ratio of Cr to Sb is (0.005-0.05): 1.
4. the method for preparing trivalent chromium ion doped fluoroantimonate near infrared fluorescent material according to claim 1, wherein the Sb source is Sb 2 O 3 Or Sb (CH) 3 COO) 3 ；
The Cr source is Cr (NO) 3 ) 3 ·9H 2 O or Cr 2 O 3 ；
The Na source is NaF, naHF 2 And Na (Na) 2 CO 3 One of the following;
the mass fraction of the HF solution is 20-60wt%.
5. The method for preparing the trivalent chromium ion doped fluoroantimonate near infrared fluorescent material according to claim 1, wherein the mixed solution is filled into a high-pressure reaction kettle, reacted for 6-15 hours at 180-220 ℃, cooled, washed and dried to obtain a finished product.
6. The method for preparing a trivalent chromium ion doped fluoroantimonate near infrared fluorescent material according to claim 1, wherein in the washing and drying process, deionized water is used for washing 1-3 times, then an organic solvent is used for washing 1-2 times to remove reaction liquid remained on the surface, and then drying is completed at the temperature of 50-100 ℃.
7. A trivalent chromium ion doped fluoroantimonate near infrared fluorescent material, which is characterized by being prepared by the preparation method of the trivalent chromium ion doped fluoroantimonate near infrared fluorescent material according to any one of claims 1 to 6.
8. The trivalent chromium ion doped fluoroantimonate near infrared fluorescent material according to claim 1, wherein the trivalent chromium ion doped fluoroantimonate near infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm to emit broadband near infrared light with the wavelength of 700-900nm, the strongest wavelength is 760-770 nm, the half-peak width is 110-120 nm, and the quantum efficiency is 53-55%.
9. The LED light source is characterized by being prepared by the following steps:
uniformly mixing the trivalent chromium ion doped fluoroantimonate near infrared luminescent fluorescent material according to claim 7 or 8 with epoxy resin to obtain a mixed material;
and coating the mixed material on a blue light LED chip, and curing to obtain the LED light source.
10. The LED light source of claim 9, wherein the trivalent chromium ion doped fluoroantimonate near infrared luminescent fluorescent material and epoxy are mixed according to a ratio of 1: mixing the components (1-4) in a mass ratio.
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