CN113444522A - Cr (chromium)3+Doped novel fluoride near-infrared fluorescent material, preparation method and luminescent light source thereof - Google Patents
Cr (chromium)3+Doped novel fluoride near-infrared fluorescent material, preparation method and luminescent light source thereof Download PDFInfo
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000011651 chromium Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052804 chromium Inorganic materials 0.000 title claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 4
- 239000000243 solution Substances 0.000 claims abstract description 33
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 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 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910021563 chromium fluoride Inorganic materials 0.000 claims abstract description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 3
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000295 emission spectrum Methods 0.000 claims description 10
- 230000005284 excitation Effects 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000002245 particle Substances 0.000 claims description 4
- -1 oxide Chemical compound 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 13
- 238000001514 detection method Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000004297 night vision Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
- 239000005428 food component Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 238000003384 imaging method Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/685—Aluminates; Silicates
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- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Abstract
The invention discloses Cr3+Doped novel fluoride near-infrared fluorescent material, preparation method and luminescent light source thereof, wherein the chemical formula of the material is ABC1‑xF6:xCr3+(ii) a A represents one or more of Li, Na, K, Rb and Cs; b represents one or more of Ca, Sr, Ba and Mg; c represents one or more of Sc, Y, Gd, La, Lu, In, Al and Ga; wherein x =0.1% -100%, A: B: C: F: Cr =1:1 (1-x) 6: x. The preparation method comprises the following steps: s1, dissolving at least one of fluoride or fluorine hydride of A and B in a fluorine-containing acidic aqueous solution according to a stoichiometric ratio to prepare a solution A; s2 fluoride of C in stoichiometric ratioOr at least one oxide, inorganic salt (one or more of chromium chloride, chromium nitrate, chromium hydroxide and chromium fluoride) or at least one oxide (chromium oxide) of Cr are dissolved in an HF aqueous solution to prepare a solution B; s3, stirring and mixing the solution A and the solution B uniformly, and transferring the mixture into a hydrothermal reaction kettle to keep the temperature for hours at a certain temperature; s4, washing, centrifuging, drying and sieving the resultant to obtain Cr3+Doped novel fluoride near-infrared fluorescent materials. The preparation method is simple to operate and suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of fluoride near-infrared fluorescent powder for blue light LED excitation, in particular to Cr3+A doped novel fluoride near-infrared fluorescent material, a preparation method and a luminescent light source thereof belong to the field of preparation of inorganic functional materials.
Background
With the rapid popularization of optical devices and consumer electronics, compact, portable, rapidly analyzable, small continuous broadband near-infrared emitting light sources are designed and can be widely applied in the fields of biosensing, food analysis, night vision illumination, plant illumination and the like. Compared with the traditional near-infrared light source and laser, the near-infrared pc-LEDs light source has the remarkable advantages of compact structure (small volume), long service life, low manufacturing cost, adjustable broadband spectral distribution and the like, and has very remarkable advantages in application to miniaturized near-infrared detection equipment.
In recent years, the osrong company firstly shows the prospect of the near-infrared fluorescent powder in the aspect of portable detection application, and small-sized portable detection equipment is manufactured to analyze food components conveniently and quickly. Then researchers successively reported the transition metal Cr3+Excited oxide system near infrared fluorescent material due to Cr3+The electronic configuration of the outermost layer is 3d3，Cr3+Based on the design principle that ions can generate broadband near-infrared emission more easily in weak octahedral crystal field, a great amount of Cr is reported3+Doped oxideThe system has a wider near infrared emission spectrum, and has higher photoelectric conversion efficiency when being applied to NIR-LEDs. However, to further expand the application field of near-infrared pc-LED devices, the near-infrared phosphor still needs to exhibit good thermal stability. The phonon energy of the fluoride system fluorescent material is lower than that of the oxide, Cr3+The d-d transition of (A) is less influenced by electron-phonon coupling in the system, so that Cr3+Has good thermal stability in fluoride system fluorescent powder. 2019, literature [ Yu, D.et al, Non-rare-earth Na3AlF6:Cr3+phosphors for far-red light-emitting diodes.ACS applied electronic materials 2019,1(11),2325-2333.]And [ Lee, C.et al, chromium (III) -doped fluoride phosphors with branched bands and isolated for light-emitting diodes. organic chemistry 2019,59(1), 376-.]Sequentially report Na3AlF6:Cr3+、K3AlF6:Cr3+And K3GaF6:Cr3+However, the above system has disadvantages of low internal quantum efficiency and poor photoelectric conversion efficiency. In recent two years, the literature [ Song, e.et al, Cr3+-Doped Sc-Based Fluoride Enabling Highly Efficient Near Infrared Luminescence:A Case Study of K2NaScF6:Cr3+.Laser&Photonics Reviews 2021,15(2),2000410]And [ Yu, H.et al.Broadband near-isolated emission of K3ScF6:Cr3+phosphors for night vision imaging system sources.Chemical Engineering Journal 2021,129271.]Two novel scandium-containing fluoride near-infrared phosphor systems (K) have also been reported2NaScF6:Cr3+And K3ScF6:Cr3+) However, the application of the method in the fields of food detection and the like is limited due to the narrow bandwidth of the emission spectrum.
Based on this, a novel Cr having high quantum efficiency, high thermal stability and broadband emission was developed3+The activated near-infrared fluoride fluorescent powder can expand the large-scale application of the fluorescent powder in the near-infrared field, and has important practical significance.
Disclosure of Invention
The present invention is directed to provide Cr which overcomes the above-mentioned disadvantages of the prior art3+The doped novel fluoride near-infrared fluorescent material has the advantages of wide emission spectrum bandwidth, high quantum efficiency and good thermal stability under the excitation of a blue light LED; meanwhile, the invention provides a preparation method of the material, and the material is prepared by a hydrothermal synthesis method, so that the particle morphology of the fluorescent powder is greatly improved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
cr (chromium)3+The doped novel fluoride near-infrared fluorescent material is characterized in that: the chemical formula of the material is ABC1-xF6:xCr3+(ii) a A represents one or more of Li, Na, K, Rb and Cs; b represents one or more of Ca, Sr, Ba and Mg; c represents one or more of Sc, Y, Gd, La, Lu, In, Al and Ga; wherein x is 0.1% -100%, A, B, C, F, Cr, 1, x, 6, x.
The invention also provides a preparation method of the material, which comprises the following steps:
s1, dissolving at least one of fluoride, fluorine hydride, chloride or nitrate of A and B in the HF aqueous solution according to the stoichiometric ratio to prepare the solution A.
S2, dissolving at least one of fluoride, oxide, chloride or nitrate, inorganic salt (one or more of chromium chloride, chromium nitrate, chromium hydroxide and chromium fluoride) or oxide (chromium oxide) of C in a stoichiometric ratio in HF aqueous solution to prepare a B solution.
S3, stirring and mixing the solution A and the solution B uniformly, and transferring the mixture into a hydrothermal reaction kettle to keep the temperature for hours at a certain temperature.
S4, washing, centrifuging and drying the resultant to obtain Cr3+Doped novel fluoride near-infrared fluorescent materials.
As an improvement to the above technical solution, Cr according to claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the concentration of the HF aqueous solution in the steps S1 and S2 is 10% -49%.
As a technical solution to the aboveThe improvement of claim 2, the Cr3+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the reaction temperature in the step S3 is 150 ℃ and 250 ℃, and the reaction time is 6-15 h.
As an improvement to the above technical solution, Cr according to claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the solvent used in the washing in the step S4 is acetic acid or alcohol, the washing is carried out for 2-5 times, the centrifugal control is 2000-4000r/min, and the drying is carried out at 70-100 ℃.
As an improvement to the above technical solution, Cr according to claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the stoichiometric ratio in steps S1 and S2 is a: B: C: F: Cr ═ 1:1 (1-x):6: x, where x is 0.1% to 100%.
As an improvement to the above technical solution, Cr according to claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: cr obtained in the step 43+The doped novel fluoride near-infrared fluorescent material has the shapes of a cube, an octahedron and the like, is uniformly distributed, and has adjustable particle size.
As an improvement to the above technical solution, Cr according to claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: cr obtained in the step 43+The emission spectrum of the doped novel fluoride near-infrared fluorescent material covers 650-1100nm broadband near-infrared emission.
Compared with the prior art, the invention has the advantages and positive effects that:
cr of the present invention3+The preparation method of the doped novel fluoride near-infrared fluorescent material adopts the fluorescent powder prepared by the simple hydrothermal synthesis method, has simple preparation method and controllable conditions, is suitable for large-scale production, and simultaneously prepares Cr3+The doped novel fluoride near-infrared fluorescent material has the near-infrared broadband emission of 650 plus 1100nm, controllable appearance, uniform particle distribution, high internal quantum efficiency and thermal stabilityThe material has good performance, and is a novel near-infrared fluorescent material which has high quality and can meet the requirement of a blue LED.
1. The fluorescent powder related by the invention comprises two wave band ranges of 250-500nm and 500-750nm, and can be efficiently excited by near ultraviolet and blue light LEDs.
2. The fluorescent powder related by the invention has the shapes of cube, octahedron and the like, is uniformly distributed, and has adjustable granularity.
3. The fluorescent powder has a broadband emission spectrum under the excitation of a near ultraviolet or blue light LED, and the manufactured LED light source has small volume, long service life, low energy consumption and stable light emission, can be applied to the fields of full spectrum illumination, night vision illumination, plant illumination and biological component detection lamps, and greatly widens the application range of the near infrared LED.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows LiSrAlF6:Cr3+XRD structure diagram of the phosphor.
FIG. 2 shows LiCaAlF6:Cr3+XRD structure diagram of the phosphor.
FIG. 3 shows LiSrGaF6:Cr3+XRD structure diagram of the phosphor.
FIG. 4 shows LiSrAlF6:Cr3+Excitation and emission spectra of the phosphor.
FIG. 5 is K3Sc0.5Y0.5F6:Cr3+Emission spectrum of the phosphor.
FIG. 6 is LiCaGaF6:Cr3+Scanning electron micrographs of the phosphors.
FIG. 7 shows LiSrScF6:Cr3+Scanning electron micrographs of the phosphors.
FIG. 8 shows a sample containing CsCaGaF6:Cr3+LED light emitting device and spectrum of fluorescent powder.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.
Examples 1 to 29 are Cr3+Doped novel fluoride near-infrared fluorescent materials and methods for their preparation are described.
Example 1
0.4354g LiF and 0.8737g CaF were weighed out2Dissolving in 20ml HF (10% -49%) water solution to prepare A solution; 1.4671g of AlF were then weighed out3And Cr (NO)3)3-9H2Dissolving O in 25ml HF (10-49%) water solution to prepare B solution; uniformly mixing the solution A and the solution B, transferring the solution A and the solution B into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle at 180 ℃, keeping the temperature for 6 hours, aging and filtering the hydrothermal reaction kettle after the reaction is finished, cleaning the hydrothermal reaction kettle for 2 to 5 times by using acetic acid or alcohol, and drying the hydrothermal reaction kettle at 70 to 100 ℃ to obtain LiCaAl0.95F6:0.05Cr3+Near-infrared fluorescent powder. Under the excitation of 450nm, the emission spectrum covers the broadband emission of 650-1100nm, and the full width at half maximum FWHM is 150.1 nm. The color coordinate is (0.7329,0.2671), the light is near infrared light, and the relative brightness is 1.0000.
Examples 2 to 10
The preparation steps are the same as example 1 except that the relevant raw materials are weighed according to the chemical formula composition and the stoichiometric amount, and the chemical formula composition, the color coordinate and the relative brightness of the product are shown in table 1.
TABLE 1 examples 2 to 12 chemical formulas, color coordinates and relative brightness
Note: the above data are obtained by testing under blue light (450nm) excitation
Example 14
0.5867g KHF were weighed out21.1411g CsF and 0.5865g CaF2、0.9436g SrF2Dissolving in 20ml HF (10% -49%) water solution to prepare A solution; 0.6893g of ScF were then weighed3、0.9385g In2O3And 0.1142g Cr2O3Dissolving in 25ml HF (10% -49%) water solution to prepare B solution; mixing the solution A and the solution B uniformly, transferring the mixture into a hydrothermal reaction kettle, heating the mixture in an oven at 220 ℃ and keeping the temperature for 10 hours, aging and filtering the mixture after the reaction is finished, cleaning the mixture for 2 to 5 times by using acetic acid or alcohol, and drying the mixture at 70 to 100 ℃ to obtain the (Cs)0.5K0.5)(Ca0.5Sr0.5)(Sc0.45In0.45)F6:0.1Cr3+Near-infrared fluorescent powder. Under the excitation of 450nm, the emission spectrum covers the broadband emission of 650-1100nm, and the full width at half maximum FWHM is 155.2 nm. The color coordinate is (0.7339,0.2671), the light is near infrared light, and the relative brightness is 1.0000.
Examples 14 to 21
The preparation procedure was the same as in example 14 except that the relevant raw materials were weighed according to their chemical formula compositions and stoichiometry, and the chemical formula compositions, color coordinates and relative brightnesses of the products are shown in table 2.
TABLE 2 examples 15 to 21 chemical formulae, color coordinates and relative brightnesses
Note: the above data are obtained by testing under blue light (450nm) excitation
Claims (10)
1. Cr (chromium)3+The doped novel fluoride near-infrared fluorescent material is characterized in that: the chemical formula of the material is ABC1- xF6: xCr3+(ii) a A represents one or more of Li, Na, K, Rb and Cs; b represents one or more of Ca, Sr, Ba and Mg; c represents one or more of Sc, Y, Gd, La, Lu, In, Al and Ga; wherein x =0.1% -100%, A: B: C: F: Cr =1:1 (1-x) 6: x.
2. Preparation of Cr as claimed in claim 13+DopingThe preparation method of the novel fluoride near-infrared fluorescent material is characterized by comprising the following steps:
s1, dissolving at least one of fluoride, fluorine hydride, chloride or nitrate of A and B in a HF aqueous solution according to a stoichiometric ratio to prepare an A solution;
s2, dissolving at least one of fluoride, oxide, chloride or nitrate, inorganic salt (one or more of chromium chloride, chromium nitrate, chromium hydroxide and chromium fluoride) or oxide (chromium oxide) of C in a stoichiometric ratio into an HF aqueous solution to prepare a B solution;
s3, stirring and mixing the solution A and the solution B uniformly, and transferring the mixture into a hydrothermal reaction kettle to keep the temperature for hours at a certain temperature;
s4, washing, centrifuging and drying the resultant to obtain Cr3+Doped novel fluoride near-infrared fluorescent materials.
3. The Cr of claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the concentration of the HF aqueous solution in the steps S1 and S2 is 10% -49%.
4. The Cr of claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the reaction temperature in the step S3 is 150 ℃ and 250 ℃, and the reaction time is 6-15 h.
5. The Cr of claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the solvent used in the washing in the step S4 is acetic acid or alcohol, the washing is carried out for 2-5 times, the centrifugal control is 2000-4000r/min, and the drying is carried out at 70-100 ℃.
6. The Cr of claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: the stoichiometric ratio in steps S1 and S2 is A: B: C: F: Cr =1:1 (1-x):6: x, wherein x =0.1% -100%.
7. The Cr of claim 23+The preparation method of the doped novel fluoride near-infrared fluorescent material is characterized by comprising the following steps: cr obtained in the step 43+The doped novel fluoride near-infrared fluorescent material has the shapes of a cube, an octahedron and the like, is uniformly distributed, and has adjustable particle size.
8. A light emitting device, characterized in that: comprising an excitation light source and the near-infrared phosphor prepared according to claims 1-7.
9. The lighting device of claim 8, wherein: the excitation light source is an LED chip covering the wavelength range of 250-500 nm.
10. The lighting device of claim 8, wherein: the emission spectrum covers a broadband near infrared emission in the wavelength range of 650-1100 nm.
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