CN107353899A - A kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application - Google Patents
A kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application Download PDFInfo
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- CN107353899A CN107353899A CN201710451605.6A CN201710451605A CN107353899A CN 107353899 A CN107353899 A CN 107353899A CN 201710451605 A CN201710451605 A CN 201710451605A CN 107353899 A CN107353899 A CN 107353899A
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- 239000000463 material Substances 0.000 title claims abstract description 115
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000005538 encapsulation Methods 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 21
- DSFLPAXQDSLSKU-UHFFFAOYSA-L [Mn](=O)(=O)(O)O.[F] Chemical compound [Mn](=O)(=O)(O)O.[F] DSFLPAXQDSLSKU-UHFFFAOYSA-L 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010583 slow cooling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 238000004383 yellowing Methods 0.000 claims description 4
- 241001062009 Indigofera Species 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910003202 NH4 Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 239000000741 silica gel Substances 0.000 abstract description 3
- 229910002027 silica gel Inorganic materials 0.000 abstract description 3
- 229910020491 K2TiF6 Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 229910004074 SiF6 Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical class [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 5
- 235000003270 potassium fluoride Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000010436 fluorite Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OJOWXSLGSMTXEO-UHFFFAOYSA-H [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] Chemical class [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] OJOWXSLGSMTXEO-UHFFFAOYSA-H 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910020440 K2SiF6 Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000303040 Glycyrrhiza glabra Species 0.000 description 1
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910003708 H2TiF6 Inorganic materials 0.000 description 1
- -1 M Si Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical class [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 235000011477 liquorice Nutrition 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 201000005111 ocular hyperemia Diseases 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/674—Halogenides
- C09K11/675—Halogenides with alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
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Abstract
The invention discloses a kind of Mn4+Doped fluoride monocrystalline red light material and preparation method and application.The Mn4+Doped fluoride monocrystalline red light material is single crystal material, and crystal particle diameter is 0.01 ~ 50 mm, chemical formula A2M1‑x F6: x Mn4+、A3T1‑x F6: x Mn4+Or BM1‑x F6: x Mn4+.The present invention prepares Mn using liquid phase volatility process, falling temperature method or hydro-thermal method is included4+Doped fluoride monocrystalline red light material, and by the Mn4+Doped fluoride monocrystalline red light material is combined encapsulation with Yellow light emitting material or green light luminescent material and blue light for InGaN chip, obtains white light LED part.Mn of the present invention4+Doped fluoride monocrystalline red light material translucency is good, is easily formed bulk and different shapes, alternative fluorescent material and epoxy resin or the composition of silica gel, can be applied to White-light LED illumination and backlight display field by widespread commercialization.
Description
Technical field
The present invention relates to LED phosphor material powder preparing technical fields, and in particular to a kind of Mn4+Doped fluoride monocrystalline is red
Luminescent material and preparation method and application.
Background technology
Compared with traditional lighting source incandescent lamp and fluorescent lamp, white light LEDs have caloric value is low, power consumption is small, response
Hurry up, without stroboscopic, long lifespan outstanding advantages of, be described as a new generation solid-state illumination light source.Current main-stream commercialization white light LEDs are by indigo plant
Light for InGaN chip and yellow fluorescent powder Y3Al5O12:Ce3+(YAG:Ce3+) combine, lack in such white light LEDs emission spectrum
Red color light component, cause the higher (CCT of device colour temperature>4000K), colour rendering index relatively low (CRI, Ra<80), it is difficult to meet room lighting
And the requirement of wide colour gamut liquid crystal display (LCD) backlight.To improve the Photochromic Properties of white light LEDs, it is necessary to be added into device
Appropriate red emitting material.
Transition metal ions Mn4+3d with uniqueness3Outer-shell electron configuration, Mn4+The fluoride red fluorescence powder of doping exists
There is stronger absorption 300~400nm near ultraviolet bands and 400~500nm blue light regions, have the sharp line in many places narrow in 610~650nm scopes
Band red emission.Its most strong absworption peak matches with blue-light LED chip emission peak (~460nm), and emission peak is sensitive positioned at naked eyes
Red light district, be preferable white light LEDs red light material.
At present, Mn has been reported4+Doped fluoride red fluorescence powder, mainly including A2MF6:Mn4+、BMF6:Mn4+Or A3NF6:
Mn4+Train type, it is most of that all there is higher luminous intensity, good heat endurance.But use Mn4+Doped fluoride
Problems be present in the LED of red fluorescence powder encapsulation：(1)Mn4+Doped fluoride red fluorescence powder meets the easy deliquescence of the water capacity, so as to lead
Device lifetime is caused to shorten；(2)Mn4+Doped fluoride red fluorescence powder is different from the rate of ageing of chip, easily causes chromaticity coordinates
Unstable, white light easily drifts about；(3) epoxy resin for being used to encapsulate either silica gel for a long time by blue light or ultraviolet radiation,
Easily occur that aging yellowing is unstable, influence the service life of white light LEDs；(4) encapsulating material is expensive, complex process, into
This is higher.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of Mn4+Doped fluoride monocrystalline feux rouges material
Material, specially a kind of fluoride single crystal red light flourescent material applied to the Mn (IV) of White-light LED illumination and backlight doping.
The Mn4+Doped fluoride monocrystalline red light material has good chemical stability, heat endurance, moisture-proof and thermal conductivity, is used for
In white light LEDs, the Photochromic Properties of white light LEDs are can effectively improve, improve the service life of white light LEDs.
The present invention also aims to provide a kind of described Mn4+The preparation method of doped fluoride monocrystalline red light material,
The preparation method includes kinds of processes, including liquid phase volatility process, falling temperature method or hydro-thermal method, and preparation technology is simple and easy, condition
Gently.
The present invention also aims to provide a kind of described Mn4+Doped fluoride monocrystalline red light material is preparing white light
Application in LED.
The purpose of the present invention is achieved through the following technical solutions.
A kind of Mn4+Doped fluoride monocrystalline red light material, it is single crystal material, crystal particle diameter is 0.01~50mm, chemistry
Formula is A2M1-xF6:xMn4+、A3T1-xF6:xMn4+Or BM1-xF6:xMn4+, wherein, A Li, Na, K, Rb, Cs and NH4In one kind or
More than one combination, one or more kinds of combinations in B Be, Mg, Ca, Sr, Ba and Zn, M Si, Ge, Sn, Ti,
One or more kinds of combinations in Zr and Hf, one or more kinds of groups in N Al, Ga, In, Bi, rare earth element
Close；X is doping Mn4+Molar percentage coefficient of the ion shared by with respect to M, T ion, 0<x<1.0.
Further, the Mn4+Doped fluoride monocrystalline red light material can effectively be excited by blue-light LED chip, 420~
Under the blue light illumination of 490nm wavelength, excite and produce the feux rouges that most strong emission peak is located at 620~640nm of wavelength.
Prepare a kind of described Mn4+The method of doped fluoride monocrystalline red light material, including liquid phase volatility process, falling temperature method or
Hydro-thermal method.
Further, Mn is prepared using liquid phase volatility process4+Doped fluoride monocrystalline red light material, specifically includes following step
Suddenly：
By Mn4+The chemical formula metering ratio of doped fluoride monocrystalline red light material, is dissolved in hydrogen by the compound of the element containing M or T
In fluorspar acid solution, AMnO is added4Permanganate or A2MnF6Fluorine manganate is reacted, and adds the compound containing A or B element,
It is eventually adding solvent to be dissolved, obtained mixed solution is placed in ventilating kitchen slowly volatilization more than 1 hour, removes solvent,
Obtained crystal obtains the Mn by washing, drying4+Doped fluoride monocrystalline red light material.
Further, Mn is prepared using falling temperature method4+Doped fluoride monocrystalline red light material, specifically comprises the following steps：
By Mn4+The chemical formula metering ratio of doped fluoride monocrystalline red light material, is dissolved in hydrogen by the compound of the element containing M or T
In fluorspar acid solution, AMnO is added4Permanganate or A2MnF6Fluorine manganate is reacted, and adds the compound containing A or B element,
It is eventually adding solvent to be dissolved, the mixed solution slow cooling that will be obtained, cooling is filtered after terminating, and obtained crystal is passed through
Washing, dry, obtain the Mn4+Doped fluoride monocrystalline red light material.
Further, the mode of the slow cooling includes being placed in the water-bath that temperature is -40~100 DEG C and dropped
Temperature.
Further, the slow cooling is to be cooled to -40~100 DEG C with 0.01~10 DEG C/min speed.
Further, Mn is prepared using hydro-thermal method4+Doped fluoride monocrystalline red light material, specifically comprises the following steps：
By Mn4+The chemical formula metering ratio of doped fluoride monocrystalline red light material, is dissolved in hydrogen by the compound of the element containing M or T
In fluorspar acid solution, AMnO is added4Permanganate or A2MnF6Fluorine manganate is reacted, and adds the compound containing A or B element,
It is eventually adding solvent to be dissolved, it is anti-that obtained mixed solution is placed in into progress hydro-thermal in Teflon inner liner stainless steel reactor
Should, reaction is filtered after terminating, and by obtained crystal by washing, drying, obtains the Mn4+Doped fluoride monocrystalline feux rouges material
Material.
Further, the temperature of the hydro-thermal reaction is 100~300 DEG C, and the time is 0.5~48h.
Further, Mn is prepared using liquid phase volatility process, falling temperature method or hydro-thermal method4+Doped fluoride monocrystalline red light material
During, described A2MnF6Fluorine manganate is prepared via a method which to obtain：
By A2MnF6The chemical formula metering ratio of fluorine manganate, the bifluoride of A fluoride or A is dissolved in into mass concentration is
In 0.01%~60% hydrofluoric acid solution, AMnO is added4, until completely dissolved, less than 5 DEG C are cooled to, quality is added dropwise
Concentration is 0.01~100.00% hydrogenperoxide steam generator until solution is filtered, will obtained by stopping immediately after purple yellowing
The yellow mercury oxide obtained is washed, dried, and obtains the A2MnF6Fluorine manganate.
Preferably, the solvent of the hydrofluoric acid solution and hydrogenperoxide steam generator be include water, inorganic acids, organic acid,
One or more kinds of combinations in alcohols, ethers, ketone and amide solvent.
Further, Mn is prepared using liquid phase volatility process, falling temperature method or hydro-thermal method4+Doped fluoride monocrystalline red light material
During, the compound of the element containing M or T is one kind in the oxide including M or T elements, halide, acid and hydrochlorate
Or more than one combination.
Further, Mn is prepared using liquid phase volatility process, falling temperature method or hydro-thermal method4+Doped fluoride monocrystalline red light material
During, add AMnO4Permanganate or A2MnF6Reaction after fluorine manganate be at a temperature of 0~100 DEG C stir 5min with
Up to solution is clarified.
Further, Mn is prepared using liquid phase volatility process, falling temperature method or hydro-thermal method4+Doped fluoride monocrystalline red light material
During, the mass ratio of the hydrofluoric acid solution and solvent is 1：0.01~1000.
Further, Mn is prepared using liquid phase volatility process, falling temperature method or hydro-thermal method4+Doped fluoride monocrystalline red light material
During, the compound containing A or B element be one kind in the halide including A or B element, oxide and hydrochlorate or
More than one combination.
Further, Mn is prepared using liquid phase volatility process, falling temperature method or hydro-thermal method4+Doped fluoride monocrystalline red light material
During, the mass concentration of the hydrofluoric acid solution is 0.01%~60%.
Further, Mn is prepared using liquid phase volatility process, falling temperature method or hydro-thermal method4+Doped fluoride monocrystalline red light material
During, the solvent of the solvent and hydrofluoric acid solution is including water, inorganic acids, organic acid, alcohols, ethers, ketone
One or more kinds of combinations in class and amide solvent.
A kind of described Mn4+Application of the doped fluoride monocrystalline red light material in white light LEDs are prepared, by the Mn4+Mix
Miscellaneous fluoride single crystal red light material is combined envelope with Yellow light emitting material or green light luminescent material and blue light for InGaN chip
Dress, obtains white light LED part.
Further, the Mn4+Doped fluoride monocrystalline red light material and Yellow light emitting material or green light luminescent material
Mass ratio be 1:0.01~100.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) Mn of the invention4+Doped fluoride monocrystalline red light material has good chemical stability, heat endurance, resistance to
Moist and thermal conductivity, in white light LEDs, can effectively improve the Photochromic Properties of white light LEDs, improve the service life of white light LEDs；
(2) Mn of the invention4+Doped fluoride monocrystalline red light material is single crystal material, and translucency is good, is easily formed big
Block and different shapes, alternative fluorescent material and epoxy resin or the composition of silica gel, can be applied to white light by widespread commercialization
LED illumination and backlight display field；
(3) preparation method of the invention includes liquid phase volatility process, falling temperature method or hydro-thermal method, and preparation is simple, bar
Part temperature, universality are wide, cost is cheap, are advantageous to large-scale industrial production；
(4) Mn of the invention4+Doped fluoride monocrystalline red light material is applied in white light LEDs are prepared, by the Mn4+Mix
Miscellaneous fluoride single crystal red light material is combined envelope with Yellow light emitting material or green light luminescent material and blue light for InGaN chip
Dress, obtains white light LED part.
Brief description of the drawings
Fig. 1 is the K prepared in embodiment 12TiF6:Mn4+The XRD diffraction patterns of monocrystalline red light material；
Fig. 2 is the K prepared in embodiment 12TiF6:Mn4+The room temperature excitation spectrum and launching light spectrogram of monocrystalline red light material；
Fig. 3 is the K prepared in embodiment 12TiF6:Mn4+Monocrystalline red light material uses visible ray and blue light in microscope
Microscopic appearance figure under irradiation；
Fig. 4 is Cs in embodiment 62SiF6:Mn4+Feux rouges crystalline material is in microscope using the shape under visible ray and blue light
Looks figure；
Fig. 5 is the electroluminescent light spectrogram of the white light LEDs encapsulated in embodiment 7.
Embodiment
Technical solution of the present invention is further elaborated below in conjunction with specific embodiments and the drawings, but following examples are only
Strengthen the explanation to technical solution of the present invention, these embodiments should not be construed to any of invention scope claimed
Limitation.
In the specific embodiment of the invention, A2MnF6The preparation process of fluorine manganate specifically comprises the following steps：
By A2MnF6The chemical formula metering ratio of fluorine manganate, takes AF or AHF2It is molten to be dissolved in the hydrofluoric acid that mass fraction is 49%
In liquid, AMnO is added4, after all dissolving, molten mixed liquor ice bath is cooled to less than 5 DEG C, is then progressively added dropwise 30wt%'s
Hydrogen peroxide, until solution is stopped being added dropwise immediately by purple yellowing, filter, gained precipitation is washed by acetone, as 80 DEG C
2h is dried, obtains A2MnF6Fluorine manganate.
In the specific embodiment of the invention, Mn4+Doped fluoride monocrystalline red light material uses liquid phase volatility process, falling temperature method or water
Prepared by hot method, specifically comprise the following steps：
By Mn4+Doped fluoride monocrystalline red light material chemical formula A2M1-xF6:xMn4+、A3T1-xF6:xMn4+Or BM1-xF6:xMn4 +Metering ratio, the oxide of tetravalence M or trivalent T elements (acid or salt) is dissolved in the hydrogen that mass concentration is 0.01%~60%
In fluorspar acid solution, AMnO is then added4Or A2MnF6, more than 5min is stirred, adds the compound containing A or B element, is stirred
30min is dissolved, and resulting solution obtains Mn by volatilization (cooling or hydro-thermal)4+Doped fluoride monocrystalline red light material.
In specific embodiment of the invention preparation process, by adjusting the dosage of raw material and solvent and species, reaction temperature, anti-
Between seasonable, so as to adjust Mn4+The luminous intensity of doped fluoride monocrystalline red light material, interior external quantum efficiency, crystal shape and big
It is small.
Embodiment 1
K2TiF6:Mn4+The preparation of monocrystalline red light material, specifically comprises the following steps：
Weigh 1ml H2TiF6It is dissolved in 50ml 1wt% hydrofluoric acid solutions, adds 0.1g potassium hexafluoromanganates and react 10 minutes；
Then 1.2g potassium fluorides are added to continue to stir 30min, gained settled solution is placed in fume hood and slowly volatilized, is volatilized by 120h
Afterwards, Mn is obtained4+Doped fluoride monocrystalline red light material, crystal is taken out and dried 2 hours as in 70 DEG C of vacuum drying chambers, is obtained
Orange-yellow crystal be final products K2TiF6:Mn4+Monocrystalline red light material.
The sample K of preparation2TiF6:Mn4+The XRD diffraction patterns of monocrystalline red light material as shown in figure 1, as shown in Figure 1, sample
Diffraction maximum and standard card JCPDS 08-0488 (K2TiF6) unanimously, the diffraction maximum of any dephasign is not observed, shows to synthesize
Fluorescent material sample be pure phase.
The sample K of preparation2TiF6:Mn4+The room temperature excitation spectrum and launching light spectrogram of monocrystalline red light material as shown in Fig. 2
As shown in Figure 2, sample has very strong broadband in ultraviolet region (320nm~390nm) and blue light area (400nm~500nm)
Excite, and in the case where 458nm light excites, the transmitting of sample is its CIE chromaticity coordinates value based on the red emission with 575~675nm
For：X=0.69, y=0.31, excitation are high.
The sample K of preparation2TiF6:Mn4+Microscopic appearance of the monocrystalline red light material under visible ray and blue light illumination such as Fig. 3 institutes
Show, find its hexagonal laminated structure of microstructure crystal, particle diameter 3-10mm, the transparent free from admixture of crystal, under blue light illumination
There is very strong red emission.
Embodiment 2
K2TiF6:Mn4+The preparation of monocrystalline red light material, specifically comprises the following steps：
Weigh 0.8g TiO2It is dissolved in 20ml hydrofluoric acid solutions (49wt%), adds 10ml acetic acid, stirred under normal temperature
60min is complete to dissolving, and adds 0.124g potassium hexafluoromanganates and reacts 10 minutes；Then 2.32g potassium fluorides are added to continue to stir
30min, resulting solution is placed in 30 DEG C of water-bath, cooled with 0.1 DEG C/min, until crystal separates out；The crystalline substance finally collected
Body is dried 4 hours as in 80 DEG C of drying boxes, and obtained orange-yellow crystal is final products K2TiF6:Mn4+Monocrystalline red light material.
The sample K of preparation2TiF6:Mn4+The diffraction of any dephasign is not observed in the XRD diffraction patterns of monocrystalline red light material
Peak, is pure phase, and sample has very strong broadband in ultraviolet region (320nm~390nm) and blue light area (400nm~500nm)
Excite, and in the case where 458nm light excites, the transmitting of sample is based on the red emission with 575~675nm；In addition, sample is visible
Yellow is presented under light, bright red is sent under blue light illumination, its hexagonal sheet of microstructure crystal is found under microscope
Structure, particle diameter 1-20mm, is evenly distributed, the transparent free from admixture of crystal.
Embodiment 3
K2TiF6:Mn4+The preparation of monocrystalline red light material, specifically comprises the following steps：
Weigh 0.8g and TiO2It is dissolved in 10ml hydrofluoric acid solutions (49wt%), adds 15ml ethanol, stirred under normal temperature
60min is complete to dissolving, and adds 0.124g potassium hexafluoromanganates and reacts 10 minutes；Then 2.32g potassium fluorides are added to continue to stir
30min, resulting solution is placed in Teflon inner liner stainless steel hydrothermal reaction kettle, 200 DEG C of hydro-thermal 12h；The crystal finally collected
Dried 4 hours as in 80 DEG C of drying boxes, obtained orange-yellow crystal is final products K2TiF6:Mn4+Monocrystalline red light material.
The sample K of preparation2TiF6:Mn4+The diffraction of any dephasign is not observed in the XRD diffraction patterns of monocrystalline red light material
Peak, is pure phase, and sample has very strong broadband in ultraviolet region (320nm~390nm) and blue light area (400nm~500nm)
Excite, and in the case where 458nm light excites, the transmitting of sample is based on the red emission with 575~675nm；In addition, sample is visible
Yellow is presented under light, bright red is sent under 450nm blue light illuminations, finds that its microstructure crystal is hexagonal under microscope
Laminated structure, particle diameter 5-10mm, is evenly distributed, the transparent free from admixture of crystal.
Embodiment 4
K2SiF6:Mn4+The preparation of monocrystalline red light material, specifically comprises the following steps：
Weigh 0.30g SiO2It is dissolved in 20ml hydrofluoric acid solutions (40wt%), 60min is stirred under normal temperature and is extremely dissolved completely,
Add 0.1g potassium permanganate reaction 60min；Then 1.16g potassium fluorides are added to continue to stir 30min, resulting solution is placed in ventilation
Cupboard volatilization 72h, collects crystal and is dried 4 hours in 80 DEG C of drying boxes, obtained orange-yellow crystal is final products K2SiF6:Mn4 +Feux rouges crystalline material.
The sample K of preparation2SiF6:Mn4+The diffraction of any dephasign is not observed in the XRD diffraction patterns of monocrystalline red light material
Peak, is pure phase, and sample has very strong broadband in ultraviolet region (320nm~390nm) and blue light area (400nm~500nm)
Excite, and in the case where 458nm light excites, the transmitting of sample is based on the red emission with 575~675nm；In addition, sample is visible
Yellow is presented under light, bright red is sent under 450nm blue light illuminations, it is in cube that its microstructure crystal is found under microscope
Shape, particle diameter 0.1-2mm, is evenly distributed, the transparent free from admixture of crystal.
Embodiment 5
K2GeF6:Mn4+The preparation of monocrystalline red light material, specifically comprises the following steps：
Weigh 0.52g GeO2It is dissolved in 20ml hydrofluoric acid solutions (40wt%), adds 5ml ethanol, stirred under normal temperature
60min is complete to dissolving, and adds 0.1g potassium permanganate reaction 60min, then adds 1.16g potassium fluorides and continues to stir 30min, will
Resulting solution is placed in 30 DEG C of water-bath, is cooled with 0.05 DEG C/min, until there is crystal precipitation.It is dry as 60 DEG C to collect crystal
Dried 4 hours in dry case, obtained orange-yellow crystal is final products K2GeF6:Mn4+Feux rouges crystalline material.
The sample K of preparation2GeF6:Mn4+The diffraction of any dephasign is not observed in the XRD diffraction patterns of monocrystalline red light material
Peak, is pure phase, and sample has very strong broadband in ultraviolet region (320nm~390nm) and blue light area (400nm~500nm)
Excite, and in the case where 458nm light excites, the transmitting of sample is based on the red emission with 575~675nm；In addition, sample is visible
Yellow is presented under light, bright red is sent under 450nm blue light illuminations, found under microscope its microstructure crystal in cube more than
Side shape, particle diameter 0.5-5mm, is evenly distributed, the transparent free from admixture of crystal.
Embodiment 6
Cs2SiF6:Mn4+The preparation of monocrystalline red light material, specifically comprises the following steps：
Measure 1ml and H2SiF6Solution is dissolved in 20ml hydrofluoric acid solutions (40wt%), adds 0.1g fluorine mangaic acid nak responses
60min；Then 3.02g cesium fluorides are added and continue to stir 30min to dissolving completely, resulting solution is placed in fume hood volatilization 72h,
Collect crystal to dry 4 hours in 80 DEG C of drying boxes, obtained orange-yellow crystal is final products Cs2SiF6:Mn4+Feux rouges crystal
Material.
The sample Cs of preparation2SiF6:Mn4+The diffraction of any dephasign is not observed in the XRD diffraction patterns of monocrystalline red light material
Peak, is pure phase, particle diameter 5-15mm, and sample has in ultraviolet region (320nm~390nm) and blue light area (400nm~500nm)
Very strong broadband excitation, and in the case where 458nm light excites, the transmitting of sample is based on the red emission with 575~675nm；Prepare
Sample Cs2SiF6:Mn4+Feux rouges Cubic Crystal Material is in microscope using microscopic appearance such as Fig. 4 under visible ray and blue light
Shown, as shown in Figure 4, particle is cubic, or polyhedral, the visible very strong red emission under blue light illumination.
Embodiment 7
The K that will be obtained in embodiment 12TiF6:Mn4+Monocrystalline red light material and Y3Al5O12:Ce (YAG) crystal combinations and indigo plant
Light for InGaN chip is packaged into white light LED part, K2TiF6:Mn4+Monocrystalline red light material and YAG mass ratio are 1:1.
The obtained electroluminescent launching light spectrogram of white light LED part is encapsulated as shown in figure 5, as shown in Figure 5, the LED devices of encapsulation
Part light efficiency under 300mA DC drivens is 120.3lm/W, colour rendering index 81, colour temperature 3560K white light.
It should be appreciated that those skilled in the art is according to true spirit of the present invention, in the specific embodiment of the invention
On the basis of any modification, replacement or the change made etc., should all cover within the scope of the present invention.
Claims (10)
- A kind of 1. Mn4+Doped fluoride monocrystalline red light material, it is characterised in that be single crystal material, crystal particle diameter is 0.01 ~ 50 Mm, chemical formula A2M1-x F6: x Mn4+、A3T1-x F6: x Mn4+Or BM1-x F6: x Mn4+, wherein, A Li, Na, K, Rb, Cs and NH4In One or more kinds of combinations, one or more kinds of combinations in B Be, Mg, Ca, Sr, Ba and Zn, M Si, One or more kinds of combinations in Ge, Sn, Ti, Zr and Hf, one kind or one kind in N Al, Ga, In, Bi, rare earth element Combination above；xTo adulterate Mn4+Molar percentage coefficient of the ion shared by with respect to M, T ion, 0<x< 1.0；The Mn4+Doped fluoride monocrystalline red light material can effectively be excited by blue-light LED chip, in the indigo plant of 420 ~ 490 nm wavelength Under light irradiation, excite and produce the feux rouges that most strong emission peak is located at the nm of wavelength 620 ~ 640.
- 2. prepare a kind of Mn described in claim 14+The method of doped fluoride monocrystalline red light material, it is characterised in that including Liquid phase volatility process, falling temperature method or hydro-thermal method.
- A kind of 3. Mn according to claim 24+The preparation method of doped fluoride monocrystalline red light material, it is characterised in that Mn is prepared using liquid phase volatility process4+Doped fluoride monocrystalline red light material, specifically comprises the following steps：By Mn4+The chemical formula metering ratio of doped fluoride monocrystalline red light material, is dissolved in hydrofluoric acid by the compound of the element containing M or T In solution, AMnO is added4Permanganate or A2MnF6Fluorine manganate is reacted, and adds the compound containing A or B element, finally Add solvent to be dissolved, obtained mixed solution is placed in ventilating kitchen slowly volatilization more than 1 hour, solvent is removed, obtains Crystal by washing, dry, obtain the Mn4+Doped fluoride monocrystalline red light material.
- A kind of 4. Mn according to claim 24+The preparation method of doped fluoride monocrystalline red light material, it is characterised in that Mn is prepared using falling temperature method4+Doped fluoride monocrystalline red light material, specifically comprises the following steps：By Mn4+The chemical formula metering ratio of doped fluoride monocrystalline red light material, is dissolved in hydrofluoric acid by the compound of the element containing M or T In solution, AMnO is added4Permanganate or A2MnF6Fluorine manganate is reacted, and adds the compound containing A or B element, finally Add solvent to be dissolved, the mixed solution slow cooling that will be obtained, cooling is filtered after terminating, by obtained crystal by washing Wash, dry, obtain the Mn4+Doped fluoride monocrystalline red light material.
- A kind of 5. Mn according to claim 44+The preparation method of doped fluoride monocrystalline red light material, it is characterised in that The mode of the slow cooling, which includes being placed in the water-bath that temperature is -40 ~ 100 DEG C, to be cooled；The slow cooling be with 0.01 ~ 10 DEG C/min speed is cooled to -40 ~ 100 DEG C.
- A kind of 6. Mn according to claim 24+The preparation method of doped fluoride monocrystalline red light material, it is characterised in that Mn is prepared using hydro-thermal method4+Doped fluoride monocrystalline red light material, specifically comprises the following steps：By Mn4+The chemical formula metering ratio of doped fluoride monocrystalline red light material, is dissolved in hydrofluoric acid by the compound of the element containing M or T In solution, AMnO is added4Permanganate or A2MnF6Fluorine manganate is reacted, and adds the compound containing A or B element, finally Add solvent to be dissolved, obtained mixed solution is placed in Teflon inner liner stainless steel reactor and carries out hydro-thermal reaction, instead Filtered after should terminating, by obtained crystal by washing, drying, obtain the Mn4+Doped fluoride monocrystalline red light material.
- A kind of 7. Mn according to claim 64+The preparation method of doped fluoride monocrystalline red light material, it is characterised in that The temperature of the hydro-thermal reaction is 100 ~ 300 DEG C, and the time is 0.5 ~ 48 h.
- 8. according to a kind of Mn described in any one of claim 3,4,64+The preparation method of doped fluoride monocrystalline red light material, its It is characterised by, the A2MnF6Fluorine manganate is prepared via a method which to obtain：By A2MnF6The chemical formula metering ratio of fluorine manganate, is dissolved in mass concentration for 0.01% by the bifluoride of A fluoride or A In ~ 60 % hydrofluoric acid solution, AMnO is added4, until completely dissolved, less than 5 DEG C are cooled to, mass concentration, which is added dropwise, is 0.01 ~ 60.00% hydrogenperoxide steam generator is until solution is filtered by stopping immediately after purple yellowing, the yellow of acquisition is sunk Form sediment and wash, dry, obtain the A2MnF6Fluorine manganate；The solvent of the hydrofluoric acid solution and hydrogenperoxide steam generator is to include water, inorganic acids, organic acid, alcohols, ethers, ketone Combination more than one or both of class and amide solvent.
- 9. according to a kind of Mn described in any one of claim 3,4,64+The preparation method of doped fluoride monocrystalline red light material, its It is characterised by, the compound of the element containing M or T is one in the oxide including M or T elements, halide, acid and hydrochlorate Kind or two or more combinations；Add AMnO4Permanganate or A2MnF6Reaction after fluorine manganate is in 0 ~ 100 DEG C of temperature 5 min of lower stirring are clarified with up to solution；The mass ratio of the hydrofluoric acid solution and solvent is 1：0.01~1000；It is described to contain A Or the compound of B element is combination more than one or both of the halide including A or B element, oxide and hydrochlorate； The mass concentration of the hydrofluoric acid solution is 0.01% ~ 60 %；The solvent of the solvent and hydrofluoric acid solution be including water, Combination more than one or both of inorganic acids, organic acid, alcohols, ethers, ketone and amide solvent.
- A kind of 10. Mn described in claim 14+Application of the doped fluoride monocrystalline red light material in white light LEDs are prepared, it is special Sign is, by the Mn4+Doped fluoride monocrystalline red light material and Yellow light emitting material or green light luminescent material and blue light InGaN chips are combined encapsulation, obtain white light LED part；The Mn4+Doped fluoride monocrystalline red light material and Yellow light emitting The mass ratio of material or green light luminescent material is 1:0.01~100.
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