CN109054814A - A kind of polynary non-lead perovskite fluorescent powder of burst of ultraviolel white light and preparation method thereof - Google Patents
A kind of polynary non-lead perovskite fluorescent powder of burst of ultraviolel white light and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 230000005284 excitation Effects 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000862 absorption spectrum Methods 0.000 abstract description 4
- 238000000695 excitation spectrum Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910021617 Indium monochloride Inorganic materials 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- -1 halide ions Chemical class 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000013456 study Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910003080 TiO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 239000002019 doping agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/626—Halogenides
- C09K11/628—Halogenides with alkali or alkaline earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7428—Halogenides
- C09K11/7435—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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- H01L33/502—Wavelength conversion materials
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Abstract
The invention discloses polynary non-lead perovskite fluorescent powder of a kind of burst of ultraviolel white light and preparation method thereof, which has perovskite structure, and chemical formula meets A2B1 xB2 1‑xB3 yB4 1‑ yX1 mX2 nX3 6‑m‑n, wherein 0≤x≤1,0≤y≤1,0 < m≤6,0 < n≤6,0≤6-m-n≤6；In addition, A is Cs+；B1、B2、B3、B4Respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Respectively F‑、Cl‑、Br‑.The present invention passes through the composition to polynary non-lead perovskite fluorescent powder key, Parameter Conditions used by the overall flow technique setting of corresponding preparation method and each step improve, near ultraviolet excitated its type of single-matrix fluorescent powder can be effectively extended compared with prior art, the function that excitation spectrum and absorption spectrum are continuously adjusted is realized, the adjusting to LED light emission color temperature is realized.
Description
Technical field
The invention belongs to field of light emitting materials, glimmering more particularly, to a kind of polynary non-lead perovskite of burst of ultraviolel white light
Light powder and preparation method thereof, the fluorescent powder especially plant the single-matrix novel inorganic non-lead of the continuously adjustable burst of ultraviolel of component
Perovskite white emitting fluorescent powder.
Background technique
Recently as expanding economy, living standard and quality are continuously improved, and the requirement to lighting source is constantly promoted,
The lighting method of energy-saving, environment-friendly and high-efficiency is increasingly by the extensive concern of each side.White light LEDs light emitting diode has small in size, energy
Consumption is less, response is fast, the service life is long, the significant advantage such as pollution-free, it is considered to be is hopeful a new generation of substitution conventional illumination sources
Lighting engineering.
Light emitting diode sheet needs thus through the mixing to different light sources as monochromatic source or cooperates excitated fluorescent powder,
So that overall spectrum is contained three source colors, stimulates the photosensory cell of human eye.White-light LED illumination relies primarily on LED chip and corresponding at present
Fluorescent powder cooperate and realize, relatively conventional and commercial extensive white light LEDs combine by blue LED and yellow fluorescent powder
It forms.The luminous color of this white light LED part can be with the variation of the thickness of driving voltage and applied fluorescent powder added by device
And change.And it is poor by current commercial white light LEDs color reducibility, colour rendering index is low, and illumination efficiency is old by blue-ray LED
Changing influences.It can be with effective solution due to indigo plant for this purpose, exciting visible fluorescence powder to obtain recombined white light by near ultraviolet LED chip
The phenomenon that a series of colour rendering indexs caused by light LED aging, colour temperature deteriorate.Therefore, it is glimmering to study near ultraviolet excitated single-matrix
Light powder is very necessary.
There is also the correlative studys of non-lead perovskite fluorescent powder, such as Sr in the prior art3Ti2O7:Eu3+、M2TiO4(M=
Ca, Sr, Ba) etc. existing non-lead perovskite fluorescent powder, these non-lead perovskite fluorescent powders although can obtain replace it is traditional
Yellow fluorescent powder, but still traditional LED can not be solved because white light is that polychromatic light mixes and the feature of bring stability difference.And
The non-lead perovskite fluorescent powder of the single matrix gone out given in the present invention can be very good to solve the problems, such as LED ageing stability, have
There is great potential market.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of burst of ultraviolel white lights
Polynary non-lead perovskite fluorescent powder and preparation method thereof, wherein passing through the composition (packet to polynary non-lead perovskite fluorescent powder key
Include the chemical element type and their proportion of composition), the overall flow technique setting of corresponding preparation method and each step
Used Parameter Conditions (temperature and time of such as sintering reaction) improve, and can effectively extend compared with prior art
Near ultraviolet excitated its type of single-matrix fluorescent powder, realizes excitation spectrum and the continuously adjustable function of absorption spectrum (swashs
The peak position of luminous spectrum can cover 380nm~630nm), using to LED light emission color temperature adjusting (colour temperature can cover 2200K~
7500K).Also, for liquid phase synthesis low yield used by the prior art, it is at high cost the problems such as, the present invention is also to preparation side
Method improves, and prepares the polynary perovskite white fluorescence material with better quality, the synthesis using solid phase synthesis process
Process costs are lower, and technological operation is simple, are suitble to large-scale production and application, are very suitable for industrial production.Due to the material
The broad-spectrum white-light generated from confinement effect (self-trapped exciton), and by B introducing Na+Ion,
Bi3+Ion come regulate and control the intensity from confinement effect, reduce perovskite in electronic latitude, to improve the polynary non-lead of the white light
The fluorescent yield of perovskite fluorescent powder realizes the white light of high quality.The new phosphors fluorescent yield that the present invention obtains is up to
90%, product purity is high and hair warm white, LED colour rendering index are up to 98, has a good application prospect.
To achieve the above object, according to one aspect of the present invention, a kind of polynary non-lead calcium of burst of ultraviolel white light is provided
Titanium ore fluorescent powder, which is characterized in that the fluorescent powder has perovskite structure, and chemical formula meets A2B1 xB2 1-xB3 yB4 1- yX1 mX2 nX3 6-m-n, wherein 0≤x≤1,0≤y≤1,0 < m≤6,0 < n≤6,0≤6-m-n≤6；In addition, A is Cs+；B1、B2、
B3、B4Respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Respectively F-、Cl-、Br-。
As present invention further optimization, its chemical formula of the fluorescent powder meets Cs2Na0.4Ag0.6InCl6、
Cs2Na0.4Ag0.6InF0.6Cl5.4、Cs2Na0.4Ag0.6InF1Cl5、Cs2Na0.4Ag0.6InF2.8Cl3.2、
Cs2Na0.4Ag0.6InF3.6Cl2.4、Cs2Na0.4Ag0.6InF6、Cs2Na0.4Ag0.6In0.99Bi0.01Cl6。
As present invention further optimization, the excitation wavelength of the fluorescent powder is 340-410nm, launch wavelength 380-
750nm；Preferably, the excitation wavelength of the fluorescent powder is 365nm.
It is another aspect of this invention to provide that glimmering the present invention provides the polynary non-lead perovskite of above-mentioned burst of ultraviolel white light is prepared
The method of light powder, which comprises the following steps:
(1) A is pressed2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nThe stoichiometric ratio of this chemical formula weighs AX powder, B respectively1X
Powder, B2X powder, B3X3Powder and B4X3Powder, wherein X is X1、X2、X3In any one；Then these powder are mutually mixed
It closes uniformly, obtained mixture of powders is precursors；
(2) precursors that the step (1) obtains are placed in crucible, heating is sintered reaction, cooling
After obtain synthesis of solid；
(3) synthesis of solid that the step (2) obtains is ground, is then replaced in crucible described in repeating
The sintering reaction in step (2) obtains synthesis of solid after cooling again；
(4) synthesis of solid for obtaining the step (3) carries out pulverization process, and it is more that burst of ultraviolel white light can be obtained
First non-lead perovskite fluorescent powder.
As present invention further optimization, in the step (2), the sintering reaction is the temperature at 360-470 DEG C
Lower progress.
As present invention further optimization, in the step (2), the sintering time of the sintering reaction is 5-10h.
As present invention further optimization, in the step (4), the pulverization process is specially ground or ball milling
Machine crushes.
Another aspect according to the invention, the present invention provides the polynary non-lead perovskite fluorescent powders of above-mentioned burst of ultraviolel white light
It is applied in fluorescent device as burst of ultraviolel substrate fluorescent powder.
As present invention further optimization, the fluorescent device is specially white light LED part, it is preferred that described ultraviolet
The polynary non-lead perovskite fluorescent powder of excited white light is to be applied jointly as burst of ultraviolel single-matrix and ultraviolet chip in the white light
In LED component.
Contemplated above technical scheme through the invention, compared with prior art, the polynary non-lead halogen in the present invention
Perovskite material A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-n(0≤x≤1,0≤y≤1,0 < m≤6,0 < n≤6,0≤6-m-n≤
6, and A is Cs+；B1、B2、B3、B4Respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Respectively F-、Cl-、Br-), contain with traditional
Lead perovskite material ABX3(A:Cs+、CH3NH3 +；B:Pb2+；X:Cl-、Br-、I-) compare, organic matter, lead element are free of, to be
A kind of novel environmental friendly material.Application for LED, white emitting fluorescent powder proposed by the present invention is, it can be achieved that single matrix warm white
Light, and possess high fluorescence quantum yield (> 80%), colour rendering index (> 90).Meanwhile the polynary non-lead in the present invention
Halogen perovskite material, B continuously can adjust B with X with arbitrary proportion1X and B2The ratio and B of X3X3And B4X3Ratio into
And continuously regulate and control the (F that X therein can be arranged for any molar ratio-、Cl-、Br-), to regulate and control the polynary non-lead perovskite material
From the power of confinement effect and quantum confined effect in material, and then it is continuously adjustable to reach fluorescent powder absorption spectrum and emission spectrum
Effect.And, it can be achieved that luminescent spectrum peak position covers 520nm~630nm, adjustable color temperature section is for regulation through the above way
2200K~7500K.
Further, the invention also provides the new opplication of polynary non-lead perovskite material, the polynary non-lead perovskite materials
Material can be applied to the fluorescent device of burst of ultraviolel, such as ultraviolet LED.We are using the polynary non-lead perovskite material as fluorescence
Powder can overcome conventional blu-ray chip to add the stabilization of the white light LED part of yellow fluorescent powder applied on the LED of burst of ultraviolel
The disadvantages of property is poor, colour rendering is poor.The polynary non-lead perovskite fluorescent powder of the burst of ultraviolel white light reported in this patent perfect can then solve
Certainly these disadvantages of conventional white light LED realize stable, high color reproduction degree white light.The fluorescent powder can be used as single matrix
Fluorescent powder application, especially have the characteristics that adjustable color, such as the fluorescent powder and ultraviolet chip can be formed white light LEDs, this
The novel white light LEDs of kind have great potential market.Also, the solid phase method simple production process reported in this patent, production
Cost is relatively low, has broad application prospects and market.In addition, in the present invention single matrix non-lead perovskite fluorescent powder, by
Then the white emitting fluorescent powder of single matrix emits white light, rather than blue light and yellow light mix and issue white light, so as to avoid because of chip
Aging, blue light weaken and bring white light color drift about the phenomenon that；That is, the single matrix gone out given in the present invention is polynary
Non-lead perovskite fluorescent powder, the problem of can solve current white light LEDs stability, advantages.
The present invention is synthesized using solid phase method, and production method is simple, environmental-friendly.Preparation method of the present invention uses solid phase
Method, using inorganic metal hal ide as raw material (A:Cs+；B1、B2: Na+、Ag+；B3、B4: In3+、Bi3+；X1、X2、X3: F-、Cl-、
Br-), it is used as presoma after being uniformly mixed and being finely ground, perovskite is made under high-temperature calcination.And as presoma, it is ground into
Powder is calcined by second, to prepare the new multicomponent non-lead perovskite white emitting fluorescent powder of high quality.
The non-lead halogen perovskite white emitting fluorescent powder AB of polynary full-inorganic in the present invention1B2B3B4X1X2X3, component company
Continue adjustable, that is, A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nMiddle x, y, m, n can consecutive variations (for example, one in the x or y takes 0
Or when 1, another can be still continuously adjusted), it is single that the fluorescent powder that these consecutive variations obtain can be used as burst of ultraviolel
Matrix.Correspondingly, in the raw material used in preparation method, one-valence-halide B1X and B2X is that arbitrary proportion is continuously adjustable,
Tri-valent metal halides B3X3And B4X3It is that arbitrary proportion is continuously adjustable, wherein X represents X1(i.e. F-)、X2(i.e. Cl-)、X3(i.e.
Br-), these three halide ions are also that arbitrary proportion is continuously adjustable；Also, one-valence-halide B1X and B2The ratio and B of X3X3
And B4X3It is independent of each other, as long as meeting B1X and B2The sum of amount of substance of X and B3X3And B4X3The sum of the amount of substance it is equal,
It and is the half of the sum of the amount of the substance of AX.
A in the present invention2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nThe polynary non-lead perovskite fluorescent powder of burst of ultraviolel white light, not only
It can change element ratio at B, be adjusted；And at X, also the innovative a variety of halide ions of introducing, pass through change
The ratio of various halide ions realizes adjustable range of the spectrum peak position from 520nm~630nm.This patent is also first simultaneously
It is a using this polynary non-lead perovskite as the fluorescent powder of burst of ultraviolel, realize what colour temperature was continuously adjusted from 2200K~7500K
White light parts.This new multicomponent perovskite system that the present invention is created, is in traditional perovskite ABX3On the basis of, pass through
It combines, has caused from confinement effect to B and to X doping, so that the half-peak breadth of traditional perovskite 60nm or so be increased
170nm or so is arrived, broad-spectrum white-light is realized.And this B and X of combined dopants, improve quantum yield, realize
Spectrum is adjustable.
For the new multicomponent non-lead perovskite fluorescent powder, the invention also provides a kind of preparation methods of solid phase method, especially
It is by preferably controlling sintering temperature and sintering time, it is only necessary to which it is ultraviolet that good target can be obtained in two-step sintering technique
The polynary non-lead perovskite fluorescent powder product of excited white light overcomes the complex process of traditional liquid phase synthesizing method, at high cost, liquid
The disadvantages of pollution.
To sum up, the polynary full-inorganic metal non-lead halogen perovskite phosphor material powder in the present invention, hair warm white, LED are aobvious
Colour index is up to 98, has a good application prospect.And the present invention proposes to be synthesized with solid phase method, energy consumption is small, yield is high,
Production cost is low and without liquid waste processing problem, perfectly solves existing use hydro-thermal method process very complicated, waste liquor contamination etc.
Drawback.Method proposed by the present invention is also more conducive to its industrially large-scale production and application.
Detailed description of the invention
Fig. 1 is A prepared by embodiment 1-72B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nX ray diffracting spectrum (its of fluorescent powder
In 0≤x≤1,0≤y≤1,0≤m≤6,0≤n≤6,0≤6-m-n≤6.In addition, A is Cs+；B1、B2、B3、B4Respectively Na+、
Ag+、In3+、Bi3+；X1、X2、X3It is respectively as follows: F-, Cl-, Br-)。
Fig. 2 is A prepared by embodiment 1-72B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nPhotoluminescence spectra (its of fluorescent powder
In 0≤x≤1,0≤y≤1,0≤m≤6,0≤n≤6,0≤6-m-n≤6.In addition, A is Cs+；B1、B2、B3、B4Respectively Na+、
Ag+、In3+、Bi3+；X1、X2、X3It is respectively as follows: F-, Cl-, Br-)。
Fig. 3 is Cs prepared by embodiment 72Na0.4Ag0.6In0.99Bi0.01Cl6The absorption spectra and emission spectra of fluorescent powder.
Fig. 4 is the Cs after the grinding of agate crucible is thin2Na0.4Ag0.6In0.99Bi0.01Cl6Fluorescent powder.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention is a kind of polynary non-lead perovskite white fluorescence of the single-matrix of burst of ultraviolel that component is continuously adjustable
Powder, the polynary non-lead perovskite white emitting fluorescent powder of the single-matrix of the burst of ultraviolel are perovskite structure, the list of the burst of ultraviolel
The expression formula of the polynary non-lead perovskite white emitting fluorescent powder of one matrix are as follows: A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-n, wherein 0≤x≤
1,0≤y≤1,0≤m≤6,0≤n≤6,0≤6-m-n≤6.In addition, A is Cs+；B1、B2、B3、B4Respectively Na+、Ag+、In3+、
Bi3+；X1、X2、X3It is respectively as follows: F-, Cl-, Br-。
The present invention carries out the preparation of above-mentioned fluorescent powder using solid phase method, method includes the following steps:
(1) B is weighed according to the mass ratio of the material x:1-x1X and B2X weighs B according to the mass ratio of the material y:1-y3X3And B4X3, together
When ensure B1X and B2The sum of amount of substance of X and B3X3And B4X3The sum of amount of substance it is equal.It weighs again and B3X3, B4X3, B1X,
B2The equal CsX of X amount of substance, base stock is uniformly mixed, and grind into powder obtains precursors；
For example, being specifically to weigh B at room temperature1X x mmol and B2X (1-x) mmol, weighs B3X3X mmol and B4X3(1-
X) mmol, then the AX of 2mmol is weighed, and be uniformly mixed, grind into powder obtains precursors.A is Cs+, B1、B2For Na+、
Ag+, B3、B4For In3+、Bi3+, X represents X1、X2、X3For F-、Cl-、Br-.Particularly, X1, X2, X3Selection can be according to required halogen
The type and ratio of anion are selected.
(2) above-mentioned precursors are placed in crucible, are subsequently placed in Muffle furnace and are warming up to temperature T, keep the temperature t hours
Afterwards, it cools to room temperature with the furnace, obtains synthesis of solid；
For example, being specifically that above-mentioned precursors are placed in crucible, 360 DEG C~470 DEG C are subsequently placed in Muffle furnace, instead
After answering 5h~10h, room temperature is cooled to the furnace, obtain synthesis of solid.
(3) white solid obtained above is regrind and is crushed, be replaced in crucible and be put into Muffle furnace repeatedly step
Rapid 2 sintering process.
(4) obtained synthetic powder is crushed, aimed perovskite white emitting fluorescent powder A can be obtained after sieving2B1 xB2 1- xB3 yB4 1-yX1 mX2 nX3 6-m-n。
The following are specific embodiments:
Embodiment 1
The preparation method of perovskite fluorescent powder in the embodiment, specific preparation process is as follows:
A) deionized water cleaning crucible 3min is used, then is dried up with nitrogen gun.
B) 0.3366g CsCl, 0.0234g NaCl, 0.0861g AgCl, 0.221g InCl are weighed3, it is uniformly mixed, uses
After mortar is finely ground, it is put into crucible.
C) crucible is placed in Muffle furnace, muffle furnace is set as 30 DEG C and rises to 460 DEG C through 1h, keeps the temperature 5h, then
It is naturally cooling to room temperature.
D) crucible in Muffle furnace is taken out, it is uniformly finely ground in mortar to take out the powder in crucible.It places into crucible, into
Row c operation.
E) crucible in Muffle furnace is taken out, takes out the powder in crucible to get Cs is arrived2Na0.4Ag0.6InCl6Fluorescent powder.
Embodiment 2
The preparation method of perovskite fluorescent powder in the embodiment, specific preparation process is as follows:
A) deionized water cleaning crucible 3min is used, then is dried up with nitrogen gun.
B) 0.3366g CsCl, 0.0234g NaCl, 0.0762g AgF, 0.221g InCl are weighed3, it is uniformly mixed, uses
After mortar is finely ground, it is put into crucible.
C) crucible is placed in Muffle furnace, muffle furnace is set as 30 DEG C and rises to 460 DEG C through 1h, keeps the temperature 5h, then
It is naturally cooling to room temperature.
D) crucible in Muffle furnace is taken out, it is uniformly finely ground in mortar to take out the powder in crucible.It places into crucible, into
Row c operation.
E) crucible in Muffle furnace is taken out, takes out the powder in crucible to get Cs is arrived2Na0.4Ag0.6InF0.6Cl5.4Fluorescence
Powder.
Embodiment 3
The preparation method of perovskite fluorescent powder in the embodiment, specific preparation process is as follows:
A) deionized water cleaning crucible 3min is used, then is dried up with nitrogen gun.
B) 0.3366g CsCl, 0.0168g NaF, 0.0762g AgF, 0.221g InCl are weighed3, it is uniformly mixed, with grinding
After alms bowl is finely ground, it is put into crucible.
C) crucible is placed in Muffle furnace, muffle furnace is set as 30 DEG C and rises to 460 DEG C through 1h, keeps the temperature 5h, then
It is naturally cooling to room temperature.
D) crucible in Muffle furnace is taken out, it is uniformly finely ground in mortar to take out the powder in crucible.It places into crucible, into
Row c operation.
E) crucible in Muffle furnace is taken out, takes out the powder in crucible to get Cs is arrived2Na0.4Ag0.6InF1Cl5Fluorescent powder.
Embodiment 4
The preparation method of perovskite fluorescent powder in the embodiment, specific preparation process is as follows:
A) deionized water cleaning crucible 3min is used, then is dried up with nitrogen gun.
B) 0.3366g CsCl, 0.0168g NaF, 0.0762g AgF, 0.0886g InCl are weighed3, 0.1032gInF3It is mixed
Close uniformly, with mortar it is finely ground after, be put into crucible.
C) crucible is placed in Muffle furnace, muffle furnace is set as 30 DEG C and rises to 460 DEG C through 1h, keeps the temperature 5h, then
It is naturally cooling to room temperature.
D) crucible in Muffle furnace is taken out, it is uniformly finely ground in mortar to take out the powder in crucible.It places into crucible, into
Row c operation.
E) crucible in Muffle furnace is taken out, takes out the powder in crucible to get Cs is arrived2Na0.4Ag0.6InF2.8Cl3.2Fluorescence
Powder.
Embodiment 5
The preparation method of perovskite fluorescent powder in the embodiment, specific preparation process is as follows:
A) deionized water cleaning crucible 3min is used, then is dried up with nitrogen gun.
B) 0.3366g CsCl, 0.0234g NaCl, 0.0762g AgF, 0.172g InF are weighed3, it is uniformly mixed, with grinding
After alms bowl is finely ground, it is put into crucible.
C) crucible is placed in Muffle furnace, muffle furnace is set as 30 DEG C and rises to 460 DEG C through 1h, keeps the temperature 5h, then
It is naturally cooling to room temperature.
D) crucible in Muffle furnace is taken out, it is uniformly finely ground in mortar to take out the powder in crucible.It places into crucible, into
Row c operation.
E) crucible in Muffle furnace is taken out, takes out the powder in crucible to get Cs is arrived2Na0.4Ag0.6InF3.6Cl2.4Fluorescence
Powder.
Embodiment 6
The preparation method of perovskite fluorescent powder in the embodiment, specific preparation process is as follows:
A) deionized water cleaning crucible 3min is used, then is dried up with nitrogen gun.
B) 0.304g CsCl, 0.0168g NaF, 0.0762g AgF, 0.172g InF are weighed3, it is uniformly mixed, uses mortar
After finely ground, it is put into crucible.
C) crucible is placed in Muffle furnace, muffle furnace is set as 30 DEG C and rises to 460 DEG C through 1h, keeps the temperature 5h, then
It is naturally cooling to room temperature.
D) crucible in Muffle furnace is taken out, it is uniformly finely ground in mortar to take out the powder in crucible.It places into crucible, into
Row c operation.
E) crucible in Muffle furnace is taken out, takes out the powder in crucible to get Cs is arrived2Na0.4Ag0.6InF6Fluorescent powder.
Embodiment 7
The preparation method of perovskite fluorescent powder in the embodiment, specific preparation process is as follows:
A) deionized water cleaning crucible 3min is used, then is dried up with nitrogen gun.
B) 0.3366g CsCl, 0.0234g NaCl, 0.0861g AgCl, 0.2193g InCl are weighed3,
0.0032gBiCl3Be uniformly mixed, with mortar it is finely ground after, be put into crucible.
C) crucible is placed in Muffle furnace, muffle furnace is set as 30 DEG C and rises to 460 DEG C through 1h, keeps the temperature 5h, then
It is naturally cooling to room temperature.
D) crucible in Muffle furnace is taken out, it is uniformly finely ground in mortar to take out the powder in crucible.It places into crucible, into
Row c operation.
E) crucible in Muffle furnace is taken out, takes out the powder in crucible to get Cs is arrived2Na0.4Ag0.6In0.99Bi0.01Cl6It is glimmering
Light powder.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of polynary non-lead perovskite fluorescent powder of burst of ultraviolel white light, which is characterized in that the fluorescent powder has perovskite structure,
Its chemical formula meets A2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-n, wherein 0≤x≤1,0≤y≤1,0 < m≤6,0 < n≤6,0≤6-
m-n≤6；In addition, A is Cs+；B1、B2、B3、B4Respectively Na+、Ag+、In3+、Bi3+；X1、X2、X3Respectively F-、Cl-、Br-。
2. the polynary non-lead perovskite fluorescent powder of burst of ultraviolel white light as described in claim 1, which is characterized in that the fluorescent powder its
Chemical formula meets Cs2Na0.4Ag0.6InCl6、Cs2Na0.4Ag0.6InF0.6Cl5.4、Cs2Na0.4Ag0.6InF1Cl5、
Cs2Na0.4Ag0.6InF2.8Cl3.2、Cs2Na0.4Ag0.6InF3.6Cl2.4、Cs2Na0.4Ag0.6InF6、
Cs2Na0.4Ag0.6In0.99Bi0.01Cl6。
3. the polynary non-lead perovskite fluorescent powder of burst of ultraviolel white light as described in claim 1, which is characterized in that the fluorescent powder
Excitation wavelength is 340-410nm, launch wavelength 380-750nm；Preferably, the excitation wavelength of the fluorescent powder is 365nm.
4. the method for preparing the polynary non-lead perovskite fluorescent powder of the burst of ultraviolel white light as described in claim 1-3 any one,
It is characterized in that, comprising the following steps:
(1) A is pressed2B1 xB2 1-xB3 yB4 1-yX1 mX2 nX3 6-m-nThe stoichiometric ratio of this chemical formula weighs AX powder, B respectively1X powder,
B2X powder, B3X3Powder and B4X3Powder, wherein X is X1、X2、X3In any one；Then these powder are mutually mixed
Even, obtained mixture of powders is precursors；
(2) precursors that the step (1) obtains are placed in crucible, heating is sintered reaction, obtains after cooling
To synthesis of solid；
(3) synthesis of solid that the step (2) obtains is ground, is then replaced in repeating said steps in crucible
(2) sintering reaction in obtains synthesis of solid after cooling again；
(4) synthesis of solid for obtaining the step (3) carries out pulverization process, and it is polynary non-that burst of ultraviolel white light can be obtained
Lead perovskite fluorescent powder.
5. method as claimed in claim 4, which is characterized in that in the step (2), the sintering reaction is at 360-470 DEG C
At a temperature of carry out.
6. method as claimed in claim 4, which is characterized in that in the step (2), the sintering time of the sintering reaction is 5-
10h。
7. method as claimed in claim 4, which is characterized in that in the step (4), the pulverization process is specially to grind
Or ball mill crushes.
8. the polynary non-lead perovskite fluorescent powder of the burst of ultraviolel white light as described in claim 1-3 any one is as burst of ultraviolel base
Matter fluorescent powder is applied in fluorescent device.
9. application as claimed in claim 8, which is characterized in that the fluorescent device is specially white light LED part, it is preferred that institute
Stating the polynary non-lead perovskite fluorescent powder of burst of ultraviolel white light is applied jointly as burst of ultraviolel single-matrix and ultraviolet chip
In the white light LED part.
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| CN112798545A (en) * | 2019-11-13 | 2021-05-14 | 中国科学院大连化学物理研究所 | Inorganic perovskite material with continuously adjustable absorption spectrum and preparation and application thereof |
| CN112798545B (en) * | 2019-11-13 | 2022-03-29 | 中国科学院大连化学物理研究所 | Inorganic perovskite material with continuously adjustable absorption spectrum and preparation and application thereof |
| CN113025327A (en) * | 2021-03-25 | 2021-06-25 | 昆明理工大学 | Multi-mode luminous lead-free double perovskite material and preparation method thereof |
| CN116656362A (en) * | 2023-06-02 | 2023-08-29 | 昆明理工大学 | Trivalent chromium ion activated broadband near infrared luminescent material and preparation method and application thereof |
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