CN107384382A - A kind of Mn4+Fluoaluminate red fluorescence powder, its preparation method and its application of doping - Google Patents
A kind of Mn4+Fluoaluminate red fluorescence powder, its preparation method and its application of doping Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 229910000590 K2MnF6 Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000000499 gel Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 229960002050 hydrofluoric acid Drugs 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000009103 reabsorption Effects 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- 230000003407 synthetizing effect Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910020440 K2SiF6 Inorganic materials 0.000 description 1
- 229910020491 K2TiF6 Inorganic materials 0.000 description 1
- 229910004883 Na2SiF6 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 102220414581 c.33A>G Human genes 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102220216906 rs1060505002 Human genes 0.000 description 1
- 102220228145 rs1064794513 Human genes 0.000 description 1
- 102220264750 rs1305455942 Human genes 0.000 description 1
- 102220012898 rs397516346 Human genes 0.000 description 1
- 102220095236 rs876658436 Human genes 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/644—Halogenides
- C09K11/645—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
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- 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+Fluoaluminate red fluorescence powder, its preparation method and the application of doping, it is as follows the step of methods described：Hydrofluoric acid and water are added in polytetrafluoroethylcontainer container, adds K2MnF6, stirring makes it add KF after dissolving；K is added after KF dissolvings3AlF6Continue to stir, treat K3AlF6Continue to stir 30min after being completely dissolved；Stand, filter after stopping stirring, take filter cake to be dried under 70 DEG C of vacuum conditions and obtain the Mn4+The fluoaluminate red fluorescence powder of doping.The present invention has advantages below compared with prior art：The present invention synthesizes K in hydrofluoric acid aqueous solution3AlF6:Mn4+Red fluorescence powder, dilute aqueous solution play purification K3AlF6The effect of thing phase purity；Pass through excessive addition KF2H2O, promote K3AlF6Mutually crystallization separates out separating-purifying to thing in aqueous；It is narrow by the phosphor emission spectral region obtained by the present invention, it efficiently avoid reabsorption phenomenon；Synthetizing phosphor powder thing is mutually pure, and luminous efficiency and collection rate are high；Its packaged white light LED part gamut range is wide.
Description
Technical field
The invention belongs to powder metallurgy and technical field of semiconductor device, more particularly to one kind should in white light LED part
Mn4+Fluoaluminate red fluorescence powder, its preparation method and the application of doping, specially K3AlF6:Mn4+Red fluorescence powder closes
Application into method and its in the encapsulation of liquid crystal flat panel display backlight LED device.
Background technology
LED (Light-emitting diodes, light emitting diode) is referred to as forth generation semiconductor green light source, has
Efficiency is high, energy consumption is low, energy-saving and environmental protection, long lifespan, reliability height, small volume, it is compact-sized, resistance to vibration is good the features such as, extensively
Led applied to traffic signals instruction, large screen flat plate display, LCD TV backlight source, outdoor scene decoration, home lighting etc.
Domain.White light LED part is mainly formed using LED chip collocation fluorescent powder packaging, and therefore, fluorescent material is the pass that LED produces white light
Key raw material, wherein red fluorescence powder are to improve white light LEDs colour rendering index with reducing the most important raw material of white light LED color temperature.
Illumination and display different application scene, have different requirements to LED fluorescent powder.For family expenses or outdoor lighting
Speech, phosphor emission spectrum is wider, and often colour rendering index is higher, and produced white light quality is higher；For LCD backlight source,
LED backlight transmitting light can will effectively pass through optical filter.For can not only not worked, on the contrary by the photon of optical filter
Add display radiating burden.As flat-panel monitor, its most important function is to provide bright in luster, bright and new beautiful height
Picture quality, then display backlight source provides white light color saturation and wants height, gamut range will width.Therefore, applied to aobvious
Show the LED fluorescent powder of device backlight, the feature should with narrow transmitting band spectrum (excitation is high) and wide gamut range.
At present, the LED red fluorescence powders applied to high-power illumination are mainly nitride red fluorescent powder CaSiAlN3:Eu2 +With Sr2Si5N8:Eu2+Deng, and CaSiAlN3:Eu2+With Sr2Si5N8:Eu2+Emission spectrum is wideband spectrum, so utilizing
CaSiAlN3:Eu2+With Sr2Si5N8:Eu2+It is difficult to the white light LED part for encapsulating out wide colour gamut and high color saturation.
Research shows that fluoride system phonon energy is low, Mn4+The transition of d-d orbital electron can launch narrow-band spectrum, because
And numerous scholars develop fluoride system red fluorescence powder one after another in recent years.The system can be excited by ultraviolet or blue light, tool
Have that feux rouges narrow emission, quantum efficiency are high, heat endurance is good, synthetic method is simple etc. a little.The Mn reported at present4+Activate fluorine
Compound system red light fluorescent powder mainly has fluosilicate (K2SiF6:Mn4+、Na2SiF6:Mn4+、KNaSiF6:Mn4+、ZnSiF6·
6H2O:Mn4+、BaSiF6:Mn4+), fluogermanate (Na2GeF6:Mn4+、K2GeF6:Mn4+、BaGeF6:Mn4+), fluostannate
(K2SnF6·H2O:Mn4+、Na2SnF6:Mn4+、Cs2SnF6:Mn4+) and fluotitanate (K2TiF6:Mn4+、Na2TiF6:Mn4+、
CsTiF6:Mn4+、BaTiF6:Mn4+) etc. system.The Mn reported4+Activation fluoride system red light fluorescent powder method mainly has wet
Chemical etching method, hydrothermal synthesis method, coprecipitation and ion-exchange.
We show past achievement in research, work as Mn4+It can launch when occupying the Al ion sites with octahedral coordination
Feux rouges (Materials Research Bulletin, 2014,60,604；Physica Status Solidi(a):
Application and Materials Science,2013,210(9),1791；Functional Materials
Letter,2013,6(3),1350028)。Mn4+With Al3+With comparable ionic radius；In solid chemical compound, ionization is determined
Effective valence link that to be ion combine to form with surrounding coordination ion of conjunction valency.Thus, if containing octahedral structure in fluoride
[AlF6] group, then utilize Mn4+Substitution Al should be able to effectively produce emitting red light.Recently, South China Science ＆ Engineering University Zhang Qin
Remote seminar reports K3AlF6:Mn4+Red fluorescence powder (ACS Appl.Mater.Interfaces, 2017,9,8805),
Above-mentioned deduction is confirmed, but it uses KF (99.5%), Al (NO3)3·9H2O (99.99%), KMnO4(AR),acetone
(AR),H2O2(30%) and HF (49%) are used as raw material, and all raw materials do not have purified, synthetic mesophase product K first2MnF6With
K3AlF6, then utilize K2MnF6And K3AlF6Carry out ion exchange synthesis red fluorescence powder.However, K3AlF6It is unstable in water,
Easily it is decomposed into K2AlF5.During using hydrofluoric acid as Ion Exchange Medium, K should be avoided3AlF6Decomposition in an aqueous medium.
The present invention develops synthesis K3AlF6:A kind of new method of Mn red fluorescence powders, using commercialization K3AlF6Voluntarily
The K of synthesis3Al5F6For raw material, but K3AlF3Industrial chemicals thing is mutually general impure.The present invention devises a collection K3Al5F6Raw material
Purification, ion exchange, supersaturation precipitation and suppression K3Al5F6The synthetic route that thing phase decomposition is integrated.Synthesized fluorescent powder product
Collection rate is high, thing is mutually pure, luminous efficiency is high, and goes out wide colour gamut white light LED part using this fluorescent powder packaging.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Mn4+The fluoaluminate red of doping is glimmering
The preparation method of light powder.
The present invention is achieved by the following technical solutions：A kind of Mn4+The preparation of the fluoaluminate red fluorescence powder of doping
Method, it is characterised in that step is as follows：Hydrofluoric acid and water are added in polytetrafluoroethylcontainer container, adds K2MnF6, stirring makes it
KF is added after dissolving；K is added after KF dissolvings3AlF6Continue to stir, treat K3AlF6Continue to stir 30min after being completely dissolved；Stop
Stand, filter after only stirring, take filter cake to be dried under 70 DEG C of vacuum conditions and obtain the Mn4+The fluoaluminate red fluorescence of doping
Powder.
As further improvement of these options, KF and K3AlF6Mol ratio be 0.4:1~6:1, K2MnF6With
K3AlF6Mol ratio be 0.02:1~0.05:1.
As further improvement of these options, KF and K3AlF6Mol ratio be 2:1, K2MnF6With K3AlF6Mole
Than for 0.03:1.
As further improvement of these options, the mass concentration of the hydrofluoric acid is 10%~40%, reaction system
The mass concentration of middle solute is 20%~50%, and the solute is K2MnF6、K3AlF6And KF.
As further improvement of these options, the mass concentration of hydrofluoric acid is 20%, the matter of solute in reaction system
It is 40% to measure concentration.
As further improvement of these options, the time of standing is 6~24h.
As further improvement of these options, the time of standing is 18h.
The present invention also provides a kind of Mn4+The fluoaluminate red fluorescence powder of doping, the Mn4+The fluoaluminate of doping is red
Fluorescent material is by any of the above-described kind of Mn4+What the preparation method of the fluoaluminate red fluorescence powder of doping prepared.
The present invention also provides above-mentioned Mn4+The white light LED part of the fluoaluminate red fluorescence powder application of doping, the LED
Device is the Mn4+The fluoaluminate red fluorescence powder of doping and β-SIALON:The green powder of Eu is mixed into AB transparent silica gels, warp
After vacuum outgas, the AB transparent silica gels for being mixed with fluorescent material are added dropwise on blue chip using point gum machine, obtained after toasted solidification
.
As further improvement of these options, the blue chip emission wavelength peak is 450nm.
The present invention has advantages below compared with prior art：The present invention synthesizes K in hydrofluoric acid aqueous solution3AlF6:Mn4+
Red fluorescence powder, dilute aqueous solution play purification K3AlF6The effect of thing phase purity；Pass through excessive addition KF2H2O, promote
K3AlF6Mutually crystallization separates out thing in aqueous, K3AlF6After crystallization separates out, other impurity are removed by filtering with the aqueous solution.This
Phosphor emission spectral region obtained by invention is narrow, and its halfwidth is about 25.88nm, and its excitation spectrum and emission spectrum are almost
There is no overlapping part, efficiently avoid reabsorption phenomenon.In addition, fluorescent material thing is mutually pure synthesized by the present invention, luminous efficiency
It is high；Synthetizing phosphor powder collection rate is high.White light LED part gamut range is wide packaged by the present invention.
Brief description of the drawings
Fig. 1 is the emission spectrum for the white light LED part that embodiment 5 obtains.
Fig. 2 is that the gamut range for the white light LED part that embodiment 5 obtains is illustrated with the comparison of the gamut ranges of NTSC 1931
Figure.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of Mn4+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that step is as follows：In polytetrafluoro
Hydrofluoric acid and water are added in ethene container, adds K2MnF6, stirring makes it add KF after dissolving；Added after KF dissolvings
K3AlF6Continue to stir, treat K3AlF6Continue to stir 30min after being completely dissolved；Stop stirring after stand 6h, filter, take filter cake in
Drying obtains the Mn under 70 DEG C of vacuum conditions4+The fluoaluminate red fluorescence powder of doping.K3AlF6In aqueous can not be steady
It is fixed to exist, decomposed K2AlF5·H2O, KF2H is added in reaction system2O helps to suppress K3AlF6Decompose so as to close
Into pure phase K3AlF6。
KF and K3AlF6Mol ratio be 0.4:1, K2MnF6With K3AlF6Mol ratio be 0.02:1.
The mass concentration of the hydrofluoric acid is 10%, and the mass concentration of solute is 20% in reaction system, and the solute is
K2MnF6、K3AlF6And KF.
Embodiment 2
A kind of Mn4+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that step is as follows：In polytetrafluoro
Hydrofluoric acid and water are added in ethene container, adds K2MnF6, stirring makes it add KF after dissolving；Added after KF dissolvings
K3AlF6Continue to stir, treat K3AlF6Continue to stir 30min after being completely dissolved；Stop stirring after stand 24h, filter, take filter cake in
Drying obtains the Mn under 70 DEG C of vacuum conditions4+The fluoaluminate red fluorescence powder of doping.K3AlF6In aqueous can not be steady
It is fixed to exist, decomposed K2AlF5·H2O, KF2H is added in reaction system2O helps to suppress K3AlF6Decompose so as to close
Into pure phase K3AlF6。
KF and K3AlF6Mol ratio be 6:1, K2MnF6With K3AlF6Mol ratio be 0.05:1.
The mass concentration of the hydrofluoric acid is 10%~40%, and the mass concentration of solute is 50% in reaction system, described
Solute is K2MnF6、K3AlF6And KF.
Embodiment 3
A kind of Mn4+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that step is as follows：In polytetrafluoro
Hydrofluoric acid and water are added in ethene container, adds K2MnF6, stirring makes it add KF after dissolving；Added after KF dissolvings
K3AlF6Continue to stir, treat K3AlF6Continue to stir 30min after being completely dissolved；Stop stirring after stand 18h, filter, take filter cake in
Drying obtains the Mn under 70 DEG C of vacuum conditions4+The fluoaluminate red fluorescence powder of doping.K3AlF6In aqueous can not be steady
It is fixed to exist, decomposed K2AlF5·H2O, KF2H is added in reaction system2O helps to suppress K3AlF6Decompose so as to close
Into pure phase K3AlF6。
KF and K3AlF6Mol ratio be 2:1, K2MnF6With K3AlF6Mol ratio be 0.03:1.The mass concentration of hydrofluoric acid
For 20%, the mass concentration of solute is 40% in reaction system.
Learnt by doing contrast test, for no addition KF2H2O sample, synthetic product are mainly K2AlF5·
2H2O；Work as KF2H2O:K3AlF6Mol ratio is from 0.4：1 increases to 1.6:When 1, K2AlF5:Mn diffraction peak intensities gradually weaken and
α-K3AlF6Diffraction peak intensity gradually strengthens；Work as KF2H2O:K3AlF6When mol ratio is greatly to 1.8, K2AlF5·2H2O dephasign diffraction
Peak has disappeared, only K3AlF6Diffraction maximum is present；But with KF2H2O:K3AlF6Mol ratio is further from 2.0:1 increases to 6.0
When, K3AlF6:Mn diffraction maximums relative intensity does not improve further, reduces on the contrary, illustrates to add excessively in synthesis material
KF·2H2O does not bring good effect.K3AlF6:Mn diffraction maximums most appear in by force KF2H2O:K3AlF6Mol ratio is 2.0:
1
Embodiment 4
A kind of Mn4+The fluoaluminate red fluorescence powder of doping, it is characterised in that：The Mn4+The fluoaluminate red of doping is glimmering
Light powder is by any Mn in such as claim 1 to 74+The preparation method of the fluoaluminate red fluorescence powder of doping prepares
's.
Embodiment 5
A kind of a kind of Mn as claimed in claim 84+The white light LEDs device of the fluoaluminate red fluorescence powder application of doping
Part, it is characterised in that：The LED component is the Mn4+The fluoaluminate red fluorescence powder of doping and β-SIALON:The green powder of Eu
It is mixed into AB transparent silica gels, after vacuum outgas, the AB transparent silica gels for being mixed with fluorescent material is added dropwise to blue light using point gum machine
On chip, obtained after toasted solidification.
The blue chip emission wavelength peak is 450nm.Packaged white light LED part emission spectrum is as shown in Figure 1.In vain
Light LED chromaticity coordinates CIE (x, y) is x=0.3226, y=0.3401；CIE (u ', v ') is u '=0.2005, v '=0.4756.
Correlated colour temperature is Tc=5949K.Color ratio：R=20.0%, G=75.9%, B=4.1%.Colour rendering index is R1=83.4, R2
=93.3, R3=60.1, R4=77.5, R5=93.9, R6=87.2, R7=78.0, R8=60.0, R9=13.6, R10=
70.0, R11=76.0, R12=62.7, R13=90.1, R14=74.1, R15=72.4, chromaticity coordinates average value Ra=79.2.
As shown in Fig. 2 the colour gamut coverage of white light LED part packaged by the present invention reaches the 96.76% of NTSC standard color scope.With
NTSC standard is compared, K3AlF6:The chromaticity coordinates scope of Mn red fluorescence powders and blue-light LED chip has expanded, but this hair
The chromaticity coordinates scope powder critical field greener than NTSC of bright used green emitting phosphor is small.
These are only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
All any modification, equivalent and improvement made within principle etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. Mn4+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that step is as follows：In polytetrafluoroethyl-ne Hydrofluoric acid and water are added in alkene container, adds K2MnF6, stirring makes it add KF after dissolving；Added after KF dissolvings K3AlF6Continue to stir, treat K3AlF6Continue to stir 30min after being completely dissolved；Stood after stopping stirring, filter, take filter cake in 70 Drying obtains the Mn under DEG C vacuum condition4+The fluoaluminate red fluorescence powder of doping.
- A kind of 2. Mn as claimed in claim 14+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that：KF With K3AlF6Mol ratio be 0.4:1~6:1, K2MnF6With K3AlF6Mol ratio be 0.02:1~0.05:1.
- A kind of 3. Mn as claimed in claim 24+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that：KF With K3AlF6Mol ratio be 2:1, K2MnF6With K3AlF6Mol ratio be 0.03:1.
- A kind of 4. Mn as claimed in claim 14+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that：Institute The mass concentration for stating hydrofluoric acid is 10%~40%, and the mass concentration of solute is 20%~50% in reaction system, the solute It is K2MnF6、K3AlF6And KF.
- A kind of 5. Mn as claimed in claim 44+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that：Hydrogen The mass concentration of fluoric acid is 20%, and the mass concentration of solute is 40% in reaction system.
- A kind of 6. Mn as claimed in claim 14+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that：It is quiet The time put is 6~24h.
- A kind of 7. Mn as claimed in claim 64+The preparation method of the fluoaluminate red fluorescence powder of doping, it is characterised in that：It is quiet The time put is 18h.
- A kind of 8. Mn4+The fluoaluminate red fluorescence powder of doping, it is characterised in that：The Mn4+The fluoaluminate red fluorescence of doping Powder is by any Mn in such as claim 1 to 74+The preparation method of the fluoaluminate red fluorescence powder of doping prepares 's.
- A kind of a kind of 9. Mn as claimed in claim 84+The white light LED part of the fluoaluminate red fluorescence powder application of doping, It is characterized in that：The LED component is the Mn4+The fluoaluminate red fluorescence powder of doping and β-SIALON:The green powder of Eu mixes Enter into AB transparent silica gels, after vacuum outgas, the AB transparent silica gels for being mixed with fluorescent material are added dropwise to blue light core using point gum machine On piece, obtained after toasted solidification.
- 10. white light LED part as claimed in claim 9, it is characterised in that：The blue chip emission wavelength peak is 450nm。
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| CN201710643508.7A CN107384382A (en) | 2017-07-31 | 2017-07-31 | A kind of Mn4+Fluoaluminate red fluorescence powder, its preparation method and its application of doping |
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Cited By (6)
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| CN108929680A (en) * | 2018-08-30 | 2018-12-04 | 合肥工业大学智能制造技术研究院 | Luminescent material for light-controlled development and preparation method thereof and light emitting device |
| CN109097031A (en) * | 2018-08-30 | 2018-12-28 | 温州大学 | A kind of Mn4+Adulterate fluoaluminic acid strontium lithium red light material and preparation method thereof |
| CN109294567A (en) * | 2018-10-18 | 2019-02-01 | 温州大学 | A kind of ammonium aluminum fluoride red light material and preparation method thereof of warm white LED tetravalence manganese ion doping |
| CN109722092A (en) * | 2018-12-20 | 2019-05-07 | 广西经正科技开发有限责任公司 | A kind of super Sensitized luminescence and preparation method of blue light excitation LED red fluorescence powder |
| CN113185971A (en) * | 2021-01-29 | 2021-07-30 | 西南政法大学 | Manganese-based fluorescent fingerprint developing powder and preparation method and application thereof |
| CN113355088A (en) * | 2021-04-30 | 2021-09-07 | 东南大学 | K2SiF6:Mn4+Preparation method of nano fluorescent powder |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929680A (en) * | 2018-08-30 | 2018-12-04 | 合肥工业大学智能制造技术研究院 | Luminescent material for light-controlled development and preparation method thereof and light emitting device |
| CN109097031A (en) * | 2018-08-30 | 2018-12-28 | 温州大学 | A kind of Mn4+Adulterate fluoaluminic acid strontium lithium red light material and preparation method thereof |
| CN109097031B (en) * | 2018-08-30 | 2021-08-31 | 温州大学 | Mn (manganese)4+Strontium lithium fluoroaluminate doped red light material and preparation method thereof |
| CN109294567A (en) * | 2018-10-18 | 2019-02-01 | 温州大学 | A kind of ammonium aluminum fluoride red light material and preparation method thereof of warm white LED tetravalence manganese ion doping |
| CN109722092A (en) * | 2018-12-20 | 2019-05-07 | 广西经正科技开发有限责任公司 | A kind of super Sensitized luminescence and preparation method of blue light excitation LED red fluorescence powder |
| CN109722092B (en) * | 2018-12-20 | 2021-11-02 | 广西经正科技开发有限责任公司 | Super-sensitization light-emitting of red fluorescent powder for blue light excited LED and preparation method thereof |
| CN113185971A (en) * | 2021-01-29 | 2021-07-30 | 西南政法大学 | Manganese-based fluorescent fingerprint developing powder and preparation method and application thereof |
| CN113185971B (en) * | 2021-01-29 | 2023-03-21 | 西南政法大学 | Manganese-based fluorescent fingerprint developing powder and preparation method and application thereof |
| CN113355088A (en) * | 2021-04-30 | 2021-09-07 | 东南大学 | K2SiF6:Mn4+Preparation method of nano fluorescent powder |
| CN113355088B (en) * | 2021-04-30 | 2022-04-12 | 东南大学 | K2SiF6:Mn4+Preparation method of nano fluorescent powder |
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