CN115785956B - Cr (chromium) 3+ Doped hexafluoroscandate near-infrared fluorescent powder and preparation method and application thereof - Google Patents
Cr (chromium) 3+ Doped hexafluoroscandate near-infrared fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000011651 chromium Substances 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052804 chromium Inorganic materials 0.000 title claims description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 7
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 28
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 26
- 150000002500 ions Chemical class 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 235000013024 sodium fluoride Nutrition 0.000 claims description 14
- 239000011775 sodium fluoride Substances 0.000 claims description 14
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 13
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 13
- -1 ammonium hexafluorochromate Chemical compound 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000005284 excitation Effects 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 229910052706 scandium Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 7
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention belongs to the technical field of luminescent materials, and discloses a Cr 3+ Doped hexafluoroscandate near infrared fluorescent powder with chemical composition of Rb 2 NaSc 1‑x F 6 :xCr 3+ Wherein x is doped Cr 3+ Relative to Sc in the matrix 3+ A mole percentage coefficient of 0<x is less than or equal to 0.07. The invention takes trivalent transition metal chromium ion as a luminescence center, and realizes the chemical formula composition of Rb by substituting trivalent chromium ion for trivalent scandium ion lattice site in matrix 2 NaSc 1‑x F 6 :xCr 3+ Absorption in the ultraviolet region, blue region and emission in the near infrared region, and Cr 3+ The doping of (a) does not alter the lattice structure of the host material.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and in particular relates to Cr 3+ Doped hexafluoroscandate near infrared fluorescent powder, and a preparation method and application thereof.
Background
The broadband near infrared light source (600-1000 nm) has important application prospect in the aspects of night vision, nondestructive detection, intelligent identification, food quality analysis, biomedical diagnosis and the like. At present, conventional Near Infrared (NIR) radiation sources mainly comprise conventional incandescent lamps and halogen lamps, but have irreparable defects of long response time, heavy volume, low efficiency and the like, which limit practical application. NIRpc-LEDs combining NIR broadband phosphors with commercial blue LED chips have received much attention because of their outstanding advantages of wavelength adjustability, high efficiency, durability, compactness, etc., as compared to conventional NIR radiation sources.
Wherein the transition metal Cr 3+ The active ion for the near infrared emission of the broadband is the most ideal active ion for the near infrared emission of the broadband at present, because the active ion has wider absorption bands in blue, orange and red light spectrum regions, the blue light absorption band is well matched with a commercial blue light chip, and the emission wavelength of the active ion has strong adjustability, so the active ion is expected to realize the near infrared emission of the broadband.
Notably, temperature is an important parameter affecting the luminescent properties of the material. At higher temperatures, the luminous intensity of the luminescent material generally decreases due to the enhancement of the non-radiative transitions; in the working state, the LED device generally accumulates a lot of heat, so that the working temperature is close to or even exceeds 150 ℃, and the fluorescence thermal stability of the luminescent material largely determines the application value.
Therefore, it is a urgent problem for those skilled in the art to provide a near infrared fluorescent powder which is matched with a blue LED chip, has high light efficiency and good thermal stability.
Disclosure of Invention
In view of this, the present invention provides a Cr 3+ The invention relates to doped hexafluoroscandate near infrared fluorescent powder, a preparation method and application thereof, wherein positive trivalent transition metal chromium ions are used as a luminescence center, and chemical formula composition Rb is realized by substituting positive trivalent chromium ions for positive trivalent scandium ion lattice sites in a matrix 2 NaSc 1-x F 6 :xCr 3+ Absorption in the ultraviolet region, blue region and emission in the near infrared region, and Cr 3+ The doping of (a) does not alter the lattice structure of the host material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
cr (chromium) 3+ The doped hexafluoroscandate near infrared fluorescent powder comprises doped ions and a matrix material; wherein the doping ion is Cr 3+ Ions, the matrix material is Rb 2 NaScF 6 ；
The dopant ions are doped in the host material to randomly replace Sc sites in the crystal.
The fluoride matrix material is an excellent luminous main body and has the characteristics of stable crystal structure, high melting point, wide energy band gap, various structural morphological characteristics and the like; cr (Cr) 3+ The ions have unique 3d 3 The outer layer electronic configuration is ideal NIR luminescence center, and can be produced by selecting proper matrix material to regulate crystal field intensity 4 T 2 → 4 A 2 Broadband near infrared emission of transitions; therefore, the invention uses the trivalent transition metal Cr 3+ For the luminous center, hexafluoroscandate Rb 2 NaScF 6 Is used as a matrix to prepare the composite material which is nontoxic, stable in chemical property and high in thermal stability (I 150℃ =92%) of a luminescent material having a chemical composition Rb 2 NaSc 1-x F 6 :xCr 3+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the anions of the matrix material are fluoride ions, the lattice structure is cubic double perovskite type, and the matrix material is prepared from [ NaF 6 ]And [ ScF ] 6 ]The dioctahedral alternate arrangement is composed of four [ NaF ] rubidium ions 6 ]And [ ScF ] 6 ]The centers of the octahedrons form a three-dimensional network structure.
Preferably, the near infrared luminescent material has a chemical formula of Rb 2 NaSc 1-x F 6 :xCr 3+ ；
Wherein x is Cr 3+ Ion relative to Sc 3+ The mole percentage coefficient of the ions is 0<x≤0.07。
Preferably, the near infrared luminescent material can generate broadband near infrared emission with the wavelength in the range of 600-1000nm under the excitation of blue light.
One of the Cr 3+ The preparation method of the doped hexafluoroscandate near infrared fluorescent powder comprises the following specific steps:
scandium oxide, rubidium carbonate, sodium fluoride and ammonium hexafluorochromate are sequentially added into hydrofluoric acid solution to react to obtain precipitate, and the precipitate is washed and dried to obtain Cr 3+ Doped hexafluoroscandate near infrared phosphor.
Preferably, the scandium oxide is stirred for 40-60min and then the rubidium carbonate is added; wherein the stirring reaction is magnetic stirring.
Preferably, the rubidium carbonate gives off a large amount of heat after being added, and the sodium fluoride is added after the solution is cooled to room temperature.
Preferably, the concentration of the hydrofluoric acid solution is 40-49wt%.
Preferably, the reaction is stirred at normal temperature for 8-10h.
Preferably, absolute ethyl alcohol is adopted for washing, and the washing times are 4 times; the drying temperature is 60-80 ℃ and the drying time is 4-8h.
The near infrared luminescent material prepared according to the near infrared luminescent material or the preparation method is applied to a blue light LED chip.
Compared with the prior art, the invention has the following beneficial effects:
1) The near infrared fluorescent powder generates a broadband near infrared emission peak under the excitation of 438nm blue light, the emission peak is positioned in the wavelength range of 600-900nm, the half-peak width is 111nm, and the strongest emission peak is positioned at 775 nm;
2) The near infrared fluorescent powder has excellent luminescence characteristic and high thermal quenching temperature (I) 150℃ =92%) and the thermal stability is far higher than most reports in the prior art, meets the actual requirements of being used with high-power pc-LED devices, and has important guiding significance for basic research and actual application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a near infrared fluorescent powder Rb prepared in examples 1 to 5 2 NaSc 1-x F 6 :xCr 3+ An XRD diffractogram of (x=0.005, 0.01, 0.03, 0.05, 0.07);
FIG. 2 is a near infrared fluorescent powder Rb prepared in example 2 2 NaSc 0.99 F 6 :0.01Cr 3+ Scanning Electron Microscope (SEM) images of (a);
FIG. 3 is a near infrared fluorescent powder Rb prepared in example 5 2 NaSc 0.93 F 6 :0.07Cr 3+ Excitation and emission spectra at room temperature;
FIG. 4 shows a near infrared fluorescent powder Rb prepared in example 3 2 NaSc 0.97 F 6 :0.03Cr 3+ A temperature-changing spectrogram within the range of 25-200 ℃;
FIG. 5 shows a near infrared fluorescent powder Rb prepared in example 1 2 NaSc 0.995 F 6 :0.005Cr 3+ Matrix Rb of (2) 2 NaScF 6 Is a band diagram of (a).
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Cr (chromium) 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder specifically comprises the following steps:
(1) Firstly, weighing 35 parts of scandium oxide according to the weight, adding the scandium oxide into a 50mL plastic test tube containing 5mL of HF solution (40 wt%) and stirring at a constant speed for 40-60min under magnetic stirring until the scandium oxide is completely dissolved to form a uniform solution;
(2) Sequentially adding 110 parts of rubidium carbonate, 20 parts of sodium fluoride and 0.5 part of ammonium hexafluorochromate into the solution obtained in the step (1), stirring at a constant speed, reacting for 8 hours at room temperature, centrifugally washing for 4 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 4 hours to obtain a product Rb 2 NaSc 0.995 F 6 :0.005Cr 3+ 。
Example 2
Cr (chromium) 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder specifically comprises the following steps:
(1) Firstly, weighing 35 parts of scandium oxide according to the weight, adding the scandium oxide into a 50mL plastic test tube containing 5mL of HF solution (40 wt%) and stirring at a constant speed for 40-60min under magnetic stirring until the scandium oxide is completely dissolved to form a uniform solution;
(2) Sequentially adding 115 parts of rubidium carbonate, 20 parts of sodium fluoride and 1 part of ammonium hexafluorochromate into the solution obtained in the step (1), stirring at a constant speed, reacting for 8 hours at room temperature, centrifugally washing for 4 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 4 hours to obtain a product Rb 2 NaSc 0.99 F 6 :0.01Cr 3+ 。
Example 3
Cr (chromium) 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder specifically comprises the following steps:
(1) Firstly, weighing 35 parts of scandium oxide according to the weight, adding the scandium oxide into a 50mL plastic test tube containing 5mL of HF solution (40 wt%) and stirring at a constant speed for 40-60min under magnetic stirring until the scandium oxide is completely dissolved to form a uniform solution;
(2) Sequentially adding 110 parts of rubidium carbonate, 25 parts of sodium fluoride and 3 parts of ammonium hexafluorochromate into the solution obtained in the step (1), stirring at a constant speed, reacting for 8 hours at room temperature, centrifugally washing for 4 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 4 hours to obtain a product Rb 2 NaSc 0.97 F 6 :0.03Cr 3+ 。
Example 4
Cr (chromium) 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder specifically comprises the following steps:
(1) Firstly, weighing 35 parts of scandium oxide according to the weight, adding the scandium oxide into a 50mL plastic test tube containing 5mL of HF solution (40 wt%) and stirring at a constant speed for 40-60min under magnetic stirring until the scandium oxide is completely dissolved to form a uniform solution;
(2) Sequentially adding 120 rubidium carbonate, 25 parts of sodium fluoride and 5 parts of ammonium hexafluorochromate into the solution obtained in the step (1), stirring at a constant speed, reacting for 8 hours at room temperature, centrifugally washing for 4 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 4 hours to obtain a product Rb 2 NaSc 0.95 F 6 :0.05Cr 3+ 。
Example 5
Cr (chromium) 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder specifically comprises the following steps:
(1) Firstly, weighing 35 parts of scandium oxide according to the weight, adding the scandium oxide into a 50mL plastic test tube containing 5mL of HF solution (40 wt%) and stirring at a constant speed for 40-60min under magnetic stirring until the scandium oxide is completely dissolved to form a uniform solution;
(2) Sequentially adding 1 to the solution obtained in the step (1)15 parts of rubidium carbonate, 25 parts of sodium fluoride and 7 parts of ammonium hexafluorochromate are stirred at a constant speed, reacted for 8 hours at room temperature, centrifugally washed for 4 times by absolute ethyl alcohol and dried for 4 hours in an oven at 80 ℃ to obtain a product Rb 2 NaSc 0.93 F 6 :0.07Cr 3+ 。
FIG. 1 shows a near infrared fluorescent powder Rb prepared in examples 1 to 5 2 NaSc 1-x F 6 :xCr 3+ As can be seen from FIG. 1, the diffraction peak of the XRD diffraction pattern of (C) is equal to that of the matrix Rb 2 NaScF 6 The diffraction peaks of the standard card (JCPDS No. 24-0970) completely correspond to each other, which shows that the synthesized sample is pure phase, no impurity phase and extra diffraction peak are generated, cr 3+ Does not change the lattice structure of the matrix;
FIG. 2 is a near infrared fluorescent powder Rb prepared in example 2 2 NaSc 0.99 F 6 :0.01Cr 3+ As can be seen from fig. 2, the sample has good crystallinity, smooth surface, irregular oblate shape, and square particles with different sizes attached;
FIG. 3 is a near infrared fluorescent powder Rb prepared in example 5 2 NaSc 0.93 F 6 :0.07Cr 3+ As can be seen from fig. 3, two distinct broadband excitation peaks can be observed in the wavelength range of 400-700 nm; under the excitation of 438nm blue light, a broadband emission peak with a half-width of 111nm and the strongest emission at 775nm can be observed in the wavelength range of 600-900 nm;
FIG. 4 shows a near infrared fluorescent powder Rb prepared in example 3 2 NaSc 0.97 F 6 :0.03Cr 3+ As can be seen from the temperature-changing spectrogram in the range of 25-200 ℃, when the working temperature is 150 ℃, the final luminous intensity still keeps 92% of the room temperature value, which indicates that the luminescent material has good thermal quenching resistance;
FIG. 5 is a near infrared fluorescent powder Rb prepared by the same method as in example 1 2 NaSc 0.995 F 6 :0.005Cr 3+ Matrix Rb of (2) 2 NaScF 6 As shown in FIG. 5, the calculation result shows that the direct band gap of the material is 6.838eV, and the wide band gap canTo provide enough space to accommodate impurity level, also can be Cr 3+ Provides a suitable environment for the emission of stable Cr 3+ Is indicative of Cr 3+ Can be successfully doped into a luminescent matrix.
Comparative example 1
Cr (chromium) 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder specifically comprises the following steps:
(1) Firstly, weighing 30 parts of scandium oxide according to the weight, adding the scandium oxide into a 50mL plastic test tube containing 5mL of HF solution (40 wt%) and stirring at a constant speed for 40-60min under magnetic stirring until the scandium oxide is completely dissolved to form a uniform solution;
(2) Sequentially adding 105 parts of rubidium fluoride, 20 parts of sodium fluoride and 3 parts of ammonium hexafluorochromate into the solution obtained in the step (1), stirring at a constant speed, reacting for 8 hours at room temperature, centrifugally washing for 4 times by using absolute ethyl alcohol, and drying in an oven at 80 ℃ for 4 hours to obtain a product Rb 2 NaSc 0.97 F 6 :0.03Cr 3+ 。
Compared with rubidium fluoride source used in comparative example 1, the raw material rubidium carbonate used in the invention has cheaper price, and effectively reduces the cost; for the preparation process of the prior art schemes such as oil bath, hydrothermal and high-temperature solid phase method, the ion exchange method is simple and convenient to operate, and the reaction process of high temperature and high pressure is avoided. In addition, the luminous property and fluorescence thermal stability of the fluorescent dye are obviously improved and enhanced, in particular Rb 2 NaScF 6 :Cr 3+ The luminous intensity at 150℃was 92% of the value at room temperature.
Comparative example 2
Cr (chromium) 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder specifically comprises the following steps:
(1) Firstly, weighing 35 parts of scandium oxide according to the weight, adding the scandium oxide into a 50mL plastic test tube containing 5mLHF solution (40 wt%) and stirring at a constant speed for 40-60min under magnetic stirring until the scandium oxide is completely dissolved to form a uniform solution;
(2) 110 parts of rubidium fluoride, 20 parts of sodium fluoride and 3 parts of ammonium hexafluorochromate are sequentially added into the solution obtained in the step (1), uniformly stirred, reacted for 12 hours at room temperature, and anhydrous is usedCentrifugally washing with ethanol for 4 times, and drying in an oven at 80 ℃ for 4 hours to obtain the product Rb 2 NaSc 0.97 F 6 :0.03Cr 3+ 。
As is clear from comparative example 2, the reaction time was prolonged to 12 hours, and the stirring time was too long, which resulted in slight concentration quenching, more center ions were replaced with luminescent center chromium ions, and the room temperature luminous intensity of the prepared phosphor was reduced by 7% as compared with example 1.
The various embodiments are described in a progressive manner, each embodiment focusing on differences from the other embodiments, and identical and similar parts between the various embodiments are sufficient to be seen with each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. Cr (chromium) 3+ The doped hexafluoroscandate near infrared fluorescent powder is characterized by comprising doped ions and a matrix material; wherein the doping ion is Cr 3+ Ions, the matrix material is Rb 2 NaScF 6 ；
The doped ions are doped in the matrix material to randomly replace Sc positions in the crystal;
the chemical general formula of the near infrared luminescent material is Rb 2 NaSc x1- F 6 :xCr 3+ ；
Wherein,xis Cr 3+ Ion relative to Sc 3+ The mole percentage coefficient of the ions is 0<x≤0.07。
2. A Cr according to claim 1 3+ Doped hexafluoroscandiumThe acid salt near infrared fluorescent powder is characterized in that the near infrared luminescent material can generate broadband near infrared emission with the wavelength in the range of 600-1000nm under the excitation of blue light.
3. A Cr according to claim 1 or 2 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder is characterized by comprising the following specific steps of:
(1) Weighing raw materials: 30-35 parts of scandium oxide, 100-120 parts of rubidium carbonate, 20-25 parts of sodium fluoride and 1-7 parts of ammonium hexafluorochromate for standby use;
(2) Scandium oxide, rubidium carbonate, sodium fluoride and ammonium hexafluorochromate are sequentially added into hydrofluoric acid solution to react for 8-10 hours to obtain precipitate, and the precipitate is washed and dried to obtain Cr 3+ Doped hexafluoroscandate near infrared phosphor.
4. A Cr according to claim 3 3+ The preparation method of the doped hexafluoroscandate near-infrared fluorescent powder is characterized in that scandium oxide is stirred for 40-60min and then rubidium carbonate is added; wherein the stirring reaction is magnetic stirring.
5. A Cr according to claim 3 3+ The preparation method of the doped hexafluoroscandate near infrared fluorescent powder is characterized in that a large amount of heat is emitted after the rubidium carbonate is added, and the sodium fluoride is added after the solution is cooled to room temperature.
6. A Cr according to claim 3 3+ The preparation method of the doped hexafluoroscandate near infrared fluorescent powder is characterized in that the concentration of the hydrofluoric acid solution is 40-49wt%.
7. A Cr according to claim 3 3+ The preparation method of the doped hexafluoroscandate near infrared fluorescent powder is characterized in that the reaction is stirring reaction for 8-10 hours at normal temperature.
8. A Cr according to claim 3 3+ The preparation method of the doped hexafluoroscandate near infrared fluorescent powder is characterized in that absolute ethyl alcohol is adopted for washing, and the washing times are 4 times; the drying temperature is 60-80 ℃ and the drying time is 4-8h.
9. Use of the near infrared phosphor according to any one of claims 1 to 2 or the near infrared phosphor prepared by the preparation method according to any one of claims 3 to 8 in a blue LED chip.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435677.9A CN115785956B (en) | 2022-11-16 | 2022-11-16 | Cr (chromium) 3+ Doped hexafluoroscandate near-infrared fluorescent powder and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435677.9A CN115785956B (en) | 2022-11-16 | 2022-11-16 | Cr (chromium) 3+ Doped hexafluoroscandate near-infrared fluorescent powder and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
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