CN106883845A - A kind of perovskite crystallite luminescent material, preparation method and applications - Google Patents

A kind of perovskite crystallite luminescent material, preparation method and applications Download PDF

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CN106883845A
CN106883845A CN201710229040.7A CN201710229040A CN106883845A CN 106883845 A CN106883845 A CN 106883845A CN 201710229040 A CN201710229040 A CN 201710229040A CN 106883845 A CN106883845 A CN 106883845A
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perovskite
luminescent material
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reaction condition
crystallite
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钟海政
陈小梅
张峰
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Beijing Institute of Technology BIT
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Abstract

The present invention provides a kind of hydridization perovskite crystallite luminescent material, and the formula of the hydridization perovskite crystallite luminescent material is A4BX6, wherein A is CH3NH3 +, NH=CHNH3 +、C(NH2)3 +Or R2NH3 +, B is any one in the metal ion of Ge, Sn, Pb, Sb, Bi, Cu or Mn, and X is Cl‑、Br‑And I‑In at least one, wherein R2The straight chain saturated alkyl group for being chain carbon atom number between 18 or saturation branched alkyl group or unsaturated linear alkyl groups or unsaturated side chain alkyl group or aromatic group.The present invention has prepared A first4BX6The organic inorganic hybridization perovskite luminescent material of type, prepared organic inorganic hybridization perovskite luminescent material luminous efficiency is high, good stability.The present invention also provides a kind of method for preparing hydridization perovskite crystallite luminescent material, the method can also be applied to prepare inorganic perovskite crystallite luminescent material simultaneously, the method is simple, highly versatile, the yield of material is high, more than 90%, impurity can be reached few, cleaning purification is easy, low cost, and material purity is high.

Description

A kind of perovskite crystallite luminescent material, preparation method and applications
Technical field
The present invention relates to Material Field, and in particular to a kind of perovskite crystallite luminescent material, preparation method and applications.
Background technology
In recent years, the appearance of metal halide perovskite material further improves people and prepares semiconductor to solwution method and receives The related understanding of rice crystalline substance or quanta point material, wherein, just it is obtained in that using simple solution manufacturing method under normal temperature condition High-quality perovskite quanta point material.Application requirement for quanta point material in display device, compared to typical II- For the InP quantum dot systems of VI races CdSe quantum dot system or iii-v, perovskite quantum dot is in luminous efficiency, half The aspect such as peak width and preparation technology suffers from bigger advantage and potentiality.For perovskite quanta point material, grind at present It is ABX to study carefully most3The perovskite quantum dot of type structure, on ABX3The preparation method of type perovskite quanta point material, structure are adjusted Control and the application report in various fields emerge in an endless stream.
Occur in that (chemical formula is Cs to the new perovskite luminescent material of a class again in nearest research report4PbBr6), this Class material has and ABX3The excellent optical property that type perovskite quantum dot is mutually equal to, with huge application potential.Particularly With the optimization and improvement of material preparation method, this kind of semi-conducting material for being referred to as zero dimension perovskite shows and ABX3Type The different special photoelectric property of perovskite (such as photoluminescence intensity is high, exciton binding energy is big).These new characteristics are caused Cs4PbBr6Application in such as light emitting diode, electroluminescent device, laser and photoelectric detector is in unprecedented Position.
From the point of view of the structure of perovskite material, perovskite material has AnBX2+nGeneral structure, the value of n determines BX6 4- The dimension of octahedral connective and perovskite：As n=1, perovskite material is typical ABX3Type three-dimensional structure (BX6 4- Octahedra corner-sharing)；As n=2, perovskite material is A2BX4Two-dimensional structure (the BX of type6 4-Octahedra plane)；As n=3, calcium Titanium ore material is one-dimentional structure (BX6 4-It is octahedra into chain)；As n=4, perovskite material is A4BX6The zero-dimension structural of type (BX6 4-Octahedron is not connected to or isolates).
But, only have Cs in current material4PbBr6Associated materials, and not organic inorganic hybridization perovskite crystallite hair Luminescent material, the same preparation method for also not having organic inorganic hybridization perovskite crystallite luminescent material.
And, existing inorganic A4BX6The preparation method of type perovskite luminescent material is mostly comparatively laborious, therefore, and it is uncomfortable For the preparation of hydridization perovskite crystallite luminescent material.It is as described below, existing inorganic A4BX6The system of type perovskite luminescent material Preparation Method is generally following several：
1. the method in the second solution is added to using the first solution, wherein the first solution is CsOA (oleic acid caesium), OA (oil Acid) and n-hexane, the second solution is PbBr2, DMF (dimethylformamide), HBr, OA and OLA (oleyl amine), what is related generally to is anti- Answer raw material more, and after adding OA, OLA so that Cs below4PbBr6The nanocrystalline purification of perovskite becomes difficult, and Fluorescence quantum yield is relatively low, and only 65% or so.
2. it is PbBr by component using the method for similar emulsion2, CsBr, DMF, OA, OLA emulsion add n-hexane it is molten In agent, the lower precipitation obtained after stirring obtains Cs with cyclohexane4PbBr6Powder (crystallite), is related to emulsion system in the method It is standby, need also exist for adding OA, OLA as emulsion stabilizer, fluorescence quantum yield is not equally high, only 40-45% or so.
3. PbBr is used2, CsBr and DMSO (dimethyl sulfoxide (DMSO)) solution system, at 50 DEG C add poor solvent acetonitrile Or methyl alcohol, the saturated solution for obtaining, continue to stir 24h, the lower precipitation as Cs for obtaining4PbBr6Powder (crystallite), fluorescent quantum Yield only has 45% or so.
4. PbBr is used2, CsBr as reaction raw materials, add DMSO as solvent, first stir a hour, after filtering again 3h is stirred after being heated to 120 DEG C, the lower precipitation for finally obtaining is dried to obtain Cs after being cleaned through DMSO4PbBr6Powder (crystallite), should The reaction time is more long in method, and DMSO has certain dissolubility to quantum dot, not good as cleaning solvent.
In sum, at present on Cs4PbBr6In the synthetic method of perovskite luminescent material, a class is made using DMSO Be solvent, by add poor solvent or heating cause reaction raw materials to reach saturation after separate out, prepare microcrystalline powder, this The reaction time of the method for kind is more long, and fluorescence quantum yield is not high, and wherein 3. method is in itself as one kind growth perovskite list The accessory substance produced in brilliant method.An other class is the preparation method of similar emulsion, using DMF as solvent, because CsBr The dissolubility difference in DMF is, it is necessary to add OA, OLA organic matter, formation emulsion is subsequently adding in poor solvent, reaction raw materials demulsification Precipitation obtains that perovskite is nanocrystalline, and the deficiency of this method is relatively cumbersome preparation method, and introduces OA, OLA Organic molecule be unfavorable for the cleaning of later stage quantum dot with purification.
Therefore, at present in A4BX6In the research of type zero dimension perovskite material, the not A on organic inorganic hybridization4BX6 Type perovskite material and corresponding preparation method.And current existing inorganic A4BX6The preparation method of type perovskite material is not It is only cumbersome, and the fluorescence quantum yield of the luminescent material for obtaining is relatively low, while obviously being also not particularly suited for preparing organic-inorganic The A of hydridization4BX6Type perovskite material.
The content of the invention
The present invention in view of the shortcomings of the prior art, proposes a kind of hydridization perovskite crystallite luminescent material and preparation method thereof, The hydridization perovskite crystallite luminescent material luminous efficiency that it is obtained is high, good stability, and its preparation method can be made on a large scale Standby and application, the preparation method can not only be applied to the preparation of hydridization perovskite crystallite luminescent material, can also equally apply In the preparation of inorganic perovskite crystallite luminescent material.
Specifically, the present invention provides a kind of hydridization perovskite crystallite luminescent material, and the hydridization perovskite crystallite lights material The formula of material is A4BX6, wherein A is CH3NH3 +, NH=CHNH3 +、C(NH2)3 +Or R2NH3 +In any one, B be Ge, Sn, Any one in the metal ion of Pb, Sb, Bi, Cu or Mn, X is Cl-、Br-And I-In at least one, wherein R2It is chain Straight chain saturated alkyl group or saturation branched alkyl group of the carbon number between 1-8 or unsaturated linear alkyl groups or not Saturation branched alkyl group or aromatic group.
Preferably, the present invention provides a kind of preparation method of hydridization perovskite crystallite luminescent material, and it is comprised the following steps：
S1, perovskite component, organic solvent constituent and catalytic component are respectively added in glass container, mixing is equal The even question response material for obtaining solid-liquid two-phase coexistent, the wherein ratio of perovskite component and organic solvent constituent are 1:(1-25)mol/ The ratio of L, catalytic component and organic solvent constituent is (0.2-0.5):1mol/L, the perovskite component is by that can be dissolved completely in The first perovskite component in organic solvent constituent and it is incompletely dissolved in the second perovskite component of organic solvent constituent and constitutes；
S2, the question response material that will be obtained in S1 are in stirring reaction condition, friction reaction condition, ultrasonic reaction condition, shake Swing and reacted under the one or more of which reaction condition in reaction condition or heating response condition, the reaction time is 1- 60min, obtains solid material after reaction；
S3, the solid material that will be obtained in S2, are repeated using with organic solvent constituent identical organic solvent in S1 Wash, dry, finally obtain hydridization perovskite crystallite luminescent material.
Preferably, the first perovskite component is that formula is ABX in S13Perovskite material or formula be BXnMetal halide Thing, the second perovskite component is that formula is the halide of AX.
Preferably, wherein A is CH3NH3 +, NH=CHNH3 +、C(NH2)3 +Or R2NH3 +In any one, B be Ge, Sn, Any one in the metal ion of Pb, Sb, Bi, Cu or Mn, X is Cl-、Br-And I-In at least one, R2For chain carbon is former Straight chain saturated alkyl group or saturation branched alkyl group or unsaturated linear alkyl groups or unsaturation of the subnumber between 1-8 Branched alkyl group or aromatic group.
Preferably, in S1 organic solvent constituent be selected from acetonitrile, acetone, methyl ethyl ketone, 2- amylalcohols, 3- amylalcohols, propionitrile, The tert-butyl alcohol, ethylenediamine, 1,2- dichloroethanes, butanone, tert-pentyl alcohol, 2 pentanone, isoamyl ketone, dichloromethane, pyridine, methyl acetate, At least one in 4-methyl-2 pentanone, propione, ethyl acetate and diethyl carbonate.
Preferably, in S1 organic solvent constituent be selected from acetone, acetonitrile, methyl ethyl ketone, propionitrile, ethyl acetate extremely Few one kind.
Preferably, catalytic component is selected from least one in halogen acids HX, sodium halide NaX or potassium halide KX, X in S1 It is Cl-、Br-Or I-。
Preferably, the formula is ABX3Perovskite material and formula for the mol ratio of the halide of AX be 1：(2-3), The formula is BXnMetal halide and formula for the mol ratio of the halide of AX be 1:(3-4).
Preferably, the stirring reaction condition in S2 is magnetic agitation, mechanical agitation or disperses at a high speed that the wherein reaction time is 1-60min, mixing speed is 50-5000r/min.
Preferably, friction reaction condition is mechanical attrition method, and the wherein reaction time is 1-60min, and drum speed is 20- 40r/min, steel ball size is 20-60mm.
Preferably, the reaction time of ultrasonic reaction condition is 1-60min, and supersonic frequency is 20-40kHz, and power density is 0.3-1W/cm2；
Preferably, concussion reaction condition is water bath with thermostatic control concussion, and the wherein reaction time is 1-60min, and frequency of oscillation is 100-300 times/min, amplitude is 20-30mm, and bath temperature is 30-85 DEG C.
Preferably, the reaction time of heating response condition is 1-60min, and temperature range is 20-90 DEG C.
Preferably, the question response material that will be obtained in S1 in S2 is in stirring reaction condition, friction reaction condition, ultrasonic reaction Reacted under two of which reaction condition in condition, concussion reaction condition or heating response condition.
Preferably, the present invention also provides a kind of luminescent device as prepared by the hydridization perovskite crystallite luminescent material.
Preferably, the present invention also provides a kind of LCD backlight source, and the LCD backlight source includes described hair Optical device.
Preferably, the present invention also provides a kind of preparation method of inorganic perovskite crystallite luminescent material, and it includes following step Suddenly：
S1, perovskite component, organic solvent constituent and catalytic component are respectively added in glass container, mixing is equal The even question response material for obtaining solid-liquid two-phase coexistent, the wherein ratio of perovskite component and organic solvent constituent are 1:(1-25)mol/ The ratio (0.2-0.5) of L, catalytic component and organic solvent constituent:1mol/L, the perovskite component is by that can be dissolved completely in The first perovskite component in machine solvent composition and it is incompletely dissolved in the second perovskite component of organic solvent constituent and constitutes；
S2, the question response material that will be obtained in S1 are in stirring reaction condition, friction reaction condition, ultrasonic reaction condition, shake Swing and reacted under the one or more of which reaction condition in reaction condition or heating response condition, the reaction time is 1- 60min, obtains solid material after reaction；
S3, the solid material that will be obtained in S2, are repeated using with organic solvent constituent identical organic solvent in S1 Wash, dry, finally obtain hydridization perovskite crystallite luminescent material.
Preferably, the first perovskite component is that formula is MBX in S13Perovskite material or formula be BXnMetal halide Thing, the second perovskite component is that formula is the halide of MX.
Preferably, wherein M is Cs+、Ru+Or K+In any one, B for Ge, Sn, Pb, Sb, Bi, Cu or Mn metal from Any one in son, X is Cl-、Br-And I-In at least one, R2It is saturated straight chain of the chain carbon atom number between 1-8 Alkyl group or saturation branched alkyl group or unsaturated linear alkyl groups or unsaturated side chain alkyl group or aromatic group.
Preferably, organic solvent constituent is dimethylformamide or dimethylacetylamide in S1.
Preferably, catalytic component is at least one in halogen acids HX, sodium halide NaX or potassium halide KX in S1, and X is Cl-、Br-Or I-。
Preferably, the stirring reaction condition in S2 is magnetic agitation, mechanical agitation or disperses at a high speed that the wherein reaction time is 1-60min, mixing speed is 50-5000r/min.
Preferably, friction reaction condition is mechanical attrition method, and the wherein reaction time is 1-60min, and drum speed is 20- 40r/min, steel ball size is 20-60mm.
Preferably, the reaction time of ultrasonic reaction condition is 1-60min, and supersonic frequency is 20-40kHz, and power density is 0.3-1W/cm2。
Preferably, concussion reaction condition is water bath with thermostatic control concussion, and the wherein reaction time is 1-60min, and frequency of oscillation is 100-300 times/min, amplitude is 20-30mm, and bath temperature is 30-85 DEG C.
Preferably, the reaction time of heating response condition is 1-60min, and temperature range is 20-90 DEG C.
Preferably, the question response material that will be obtained in S1 in S2 is in stirring reaction condition, friction reaction condition, ultrasonic reaction Reacted under two of which reaction condition in condition, concussion reaction condition or heating response condition.
Compared with prior art, the invention has the advantages that：
1. the present invention has prepared A first4BX6Hydridization perovskite crystallite luminescent material of type and preparation method thereof, it is prepared Hydridization perovskite crystallite luminescent material A4BX6Compositional purity is high, and purity can reach more than 90%, and luminous efficiency is high, fluorescence volume Sub- yield can reach more than 80%, good stability.
2. inorganic perovskite luminescent material is prepared using preparation method of the invention, compared with other preparations Cs4PbBr6Perovskite For the method for luminescent material, the method applied in the present invention is simple, highly versatile, and the yield of material is high, can reach 90% with Upper, impurity is few, and cleaning purifies easy, cost-effective, the Cs after cleaning4PbBr6Material component purity is (purity close to 100%) high, Technique amplification easily is carried out, is easy for having been realized in the preparation of hectogram rank at present.
3. the inventive method prepare hydridization perovskite luminescent material or inorganic perovskite luminescent material when, use it is organic Solvent composition matches with perovskite component, and the perovskite component one of which of selection can be completely dissolved and be dispersed in organic solvent In component, another then can not well dissolve and be dispersed in organic component, exist in the form of solid phase, so as to form solid-liquid Two-phase coexistent body, the solid-liquid two-phase mixture of formation is started instead by stirring, friction, control that is ultrasonic, shaking or heat these conditions Should, dispersion one of which perovskite component in organic solvent is fully contacted reaction with another perovskite component of solid phase, this Planting special solid-liquid contact reaction system ensure that perovskite component reaction to A4BX6Type thaumatropy.Avoid existing technology In reaction system perovskite component have during the course of the reaction greatly to ABX3Type thaumatropy.
4. the inventive method introduces catalytic component simultaneously in the preparation, in reaction, if solid-liquid contact reaction system Simple to be carried out under stirring, friction, ultrasound, the control shaking or heat these conditions, the reaction time is more long, generally requires 30 Minute or so.And the introducing of catalytic component can promote perovskite component reaction to form A4BX6Crystallite, typically adds catalyst Whole course of reaction can be shortened to 1 minute from 30 minutes after component, substantially increase the efficiency for preparing perovskite luminescent material.
Brief description of the drawings
Fig. 1 is (NH=CHNH3)4PbBr6The fluorescence spectrum of perovskite luminescent material；
Fig. 2 is (NH=CHNH3)4PbBr6The microcosmic collection of illustrative plates of perovskite luminescent material；
Fig. 3 is (CH3NH3)4PbBr6The fluorescence spectrum of perovskite luminescent material；
Fig. 4 is Cs4PbBr6The microcosmic collection of illustrative plates of perovskite luminescent material；
Fig. 5 is Cs4PbBr6The XRD spectrum of perovskite luminescent material；
Fig. 6 is Cs4PbBr6The EDS collection of illustrative plates of perovskite luminescent material；
Fig. 7 is Cs4PbBr6The structural representation of perovskite luminescent material；And
Fig. 8 is based on (NH=CHNH3)4PbBr6The spectrum of the backlight of perovskite luminescent material.
Specific embodiment
Exemplary embodiment of the invention, feature and aspect are described in detail below with reference to accompanying drawing.Identical is attached in accompanying drawing Icon note represents the same or analogous element of function.Although the various aspects of embodiment are shown in the drawings, unless special Do not point out, it is not necessary to accompanying drawing drawn to scale.
The present invention provides a kind of hydridization perovskite crystallite luminescent material, the formula of the hydridization perovskite crystallite luminescent material It is A4BX6, wherein A is CH3NH3 +, NH=CHNH3 +、C(NH2)3 +Or R2NH3 +In any one, B be Ge, Sn, Pb, Sb, Bi, Any one in the metal ion of Cu or Mn, X is Cl-、Br-And I-In at least one, wherein R2For chain carbon atom number exists Straight chain saturated alkyl group or saturation branched alkyl group or unsaturated linear alkyl groups or unsaturated side chain alkane between 1-8 Base group or aromatic group.
The present invention also provides a kind of preparation method of perovskite crystallite luminescent material, and it is comprised the following steps：
S1, perovskite component, organic solvent constituent and catalytic component are respectively added in glass container, mixing is equal The even question response material for obtaining solid-liquid two-phase coexistent, the wherein ratio of perovskite component and organic solvent constituent are 1:(1-25)mol/ The ratio (0.2-0.5) of L, catalytic component and organic solvent constituent:1mol/L, the perovskite component is by that can be dissolved completely in The first perovskite component in machine solvent composition and it is incompletely dissolved in the second perovskite component of organic solvent constituent and constitutes；
S2, the question response material that will be obtained in S1 are in stirring reaction condition, friction reaction condition, ultrasonic reaction condition, shake Swing and reacted under the one or more of which reaction condition in reaction condition or heating response condition, the reaction time is 1- 60min, obtains solid material after reaction；
S3, the solid material that will be obtained in S2, are repeated using with organic solvent constituent identical organic solvent in S1 Wash, dry, finally obtain hydridization perovskite crystallite luminescent material.
Preferably, the first perovskite component is that formula is ABX in S13Perovskite material or formula be BXnMetal halide Thing, the second perovskite component is that formula is the halide of AX.
Stirring reaction condition in S2 is magnetic agitation, mechanical agitation or high speed are disperseed, and the wherein reaction time is 1- 60min, mixing speed is 50-5000r/min；
Friction reaction condition is mechanical attrition method, and the wherein reaction time is 1-60min, and drum speed is 20-40r/min, Steel ball size is 20-60mm；
The reaction time of ultrasonic reaction condition is 1-60min, and supersonic frequency is 20-40kHz, and power density is 0.3-1W/ cm2；
Concussion reaction condition be water bath with thermostatic control concussion, wherein the reaction time be 1-60min, frequency of oscillation be 100-300 times/ Min, amplitude is 20-30mm, and bath temperature is 30-85 DEG C；And
The reaction time of heating response condition is 1-60min, and temperature range is 20-90 DEG C.
The method can be not only used for preparing hydridization perovskite crystallite luminescent material, it is same can be used for preparing it is inorganic Perovskite crystallite luminescent material.
The present invention is further explained with reference to embodiment：
Prepare hydridization perovskite crystallite luminescent material
(the NH=CHNH of embodiment 13)4PbBr6The preparation of perovskite luminescent material
S1, by metal halide component PbBr21mmol, organic amine halogen component NH=CHNH3Br 3mmol, organic solvent Component acetonitrile 10mL is added in vial, then the ratio of perovskite component and organic solvent is (1+3):10mol/L, is 1: 2.5mol/L；
S2, the ultrasonic disperse 20min under 20 DEG C of temperature conditionss, supersonic frequency are 20kHz, and turbid solution is changed into light from yellow Green；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is cleaned with acetonitrile solvent 3 times, i.e. available (NH=CHNH after drying3)4PbBr6Green powder, material sends blue green light under 365nm ultra violet lamps, As shown in figure 1, sepectrophotofluorometer test result shows (NH=CHNH3)4PbBr6The emission wavelength of perovskite luminescent material It is 505nm, a width of 21nm of half-peak, quantum yield test result shows (NH=CHNH3)4PbBr6Perovskite luminescent material it is absolute Fluorescence quantum yield is that 85%, Fig. 2 is to prepare (the NH=CHNH for drawing3)4PbBr6In the secure execution mode (sem micro- of perovskite luminescent material See pattern.
(the CH of embodiment 23NH3)4PbBr6The preparation of perovskite luminescent material
S1, by metal halide component PbBr24mmol, organic amine halogen component CH3NH3Br 16mmol, organic solvent group Acetone 8mL is divided to be well mixed in adding rustless steel container；
S2, the steel ball for adding a diameter of 20mm, use mechanical ball mill 30min under 30 DEG C of temperature conditionss, and muddy consolidates Liquid phase is changed into light green from yellow；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is cleaned with acetone solvent 3 times, i.e. available (CH after drying3NH3)4PbBr6Green powder, material sends very strong green under 365nm ultra violet lamps Light, as shown in figure 3, sepectrophotofluorometer test result shows (CH3NH3)4PbBr6The emission wavelength of perovskite luminescent material It is 512nm, a width of 27nm of half-peak, quantum yield test result shows (CH3NH3)4PbBr6Perovskite luminescent material it is absolute glimmering Quantum yield is 80%.
(the NH=CHNH of embodiment 33)4PbI6The preparation of perovskite luminescent material
S1, by metal halide component PbI21mmol, organic amine halogen component NH=CHNH3I 3.2mmol, organic solvent Component ethyl acetate 10mL is added in vial；
S2, above-mentioned mixing solid-liquid shake 50min under the conditions of 50 DEG C of water bath with thermostatic control, and turbid solution is changed into yellowish green from yellow Color；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid ethyl acetate solvent Cleaning 3 times, i.e. available (NH=CHNH after drying3)4PbI6Yellow greenish powder, material sends under 365nm ultra violet lamps Green-yellow light, the fluorescence emission wavelengths with sepectrophotofluorometer test material are 553nm.
(the NH=CHNH of embodiment 43)4PbCl6The preparation of perovskite luminescent material
S1, by metal halide component PbCl21mmol, organic amine halogen component NH=CHNH3Cl 3.4mmol, You Jirong Agent component acetonitrile 40mL is added in vial；
S2, above-mentioned mixing solid-liquid carry out heating using microwave 35min, and turbid solution is changed into light green from yellow；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is cleaned with acetonitrile solvent 3 times, i.e. available (NH=CHNH after drying3)4PbCl6Pale green powder, material sends bluish-green under 365nm ultra violet lamps Light, the fluorescence emission wavelengths with sepectrophotofluorometer test material are 492nm.
(the C of embodiment 56H5NH3)4PbBr6The preparation of perovskite luminescent material
S1, by metal halide component PbBr21mmol, organic amine halogen component C6H5NH3Br 3.6mmol, organic solvent Component propionitrile 25mL, catalytic component HBr 7.5mmol are added in vial；
S2, above-mentioned solid-liquid body is disperseed at a high speed 5min, the scattered rotating speed of high speed under 30 DEG C of temperature conditionss 3500r/min, turbid solution is changed into light green from yellow；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is cleaned with propionitrile solvent 3 times, i.e. available (C after drying6H5NH3)4PbBr6Green powder, material sends green glow under 365nm ultra violet lamps, with glimmering The fluorescence emission wavelengths of light spectrophotometer test material are 524nm.
(the CH of embodiment 62=CHCH2CH3NH3)4PbBr6The preparation of perovskite luminescent material
S1, by metal halide component PbBr21mmol, organic amine halogen component CH2=CHCH2CH3NH3Br 3.8mmol, Organic solvent constituent methyl ethyl ketone 50mL is added in vial；
S2, by the above-mentioned solid-liquid body for mixing high-speed stirred 30min under 30 DEG C of temperature conditionss, mixing speed is 500r/min, turbid solution is changed into light green from yellow；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is molten with methyl ethyl ketone Agent is cleaned 3 times, i.e. available (CH after drying2=CHCH2CH3NH3)4PbBr6Green powder, the material under 365nm ultra violet lamps Material sends green glow, and the fluorescence emission wavelengths with sepectrophotofluorometer test material are 519nm.
(C (the NH of embodiment 72)3)4PbBr6The preparation of perovskite luminescent material
S1, by perovskite component C (NH2)3PbBr31mmol, organic amine halogen component C (NH2)3Br 2.9mmol, You Jirong Agent component methyl alcohol 20mL, catalytic component KBr 5mmol are added in vial；
S2, by the above-mentioned solid-liquid body for mixing under 30 DEG C of temperature conditionss ultrasound 3min, supersonic frequency is 30kHz, turbid solution is changed into light green from yellow；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is cleaned with methanol solvate 3 times, i.e. available (C (NH after drying2)3)4PbBr6Green powder, material sends green glow under 365nm ultra violet lamps, with glimmering The fluorescence emission wavelengths of light spectrophotometer test material are 526nm.
(C (the NH of embodiment 82)3)4MnBr6The preparation of perovskite luminescent material
S1, by perovskite component C (NH2)3MnCl31mmol, organic amine halogen component C (NH2)3Cl 2.6mmol, You Jirong Agent component methyl alcohol 20mL, catalytic component HCl 6mmol are added in vial；
S2, by the above-mentioned solid-liquid body for mixing under 30 DEG C of temperature conditionss ultrasound 8min, supersonic frequency is 30kHz, turbid solution is changed into light green from milky；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is cleaned with methanol solvate 3 times, i.e. available (C (NH after drying2)3)4MnCl6Pale green powder, material sends blue green light under 365nm ultra violet lamps, Fluorescence emission wavelengths with sepectrophotofluorometer test material are 486nm.
(the NH=CHNH of embodiment 93)4SbBr6The preparation of perovskite luminescent material
S1, by perovskite component NH=CHNH3SbBr31mmol, organic amine halogen component NH=CHNH3Br 3mmol, have Machine solvent composition methyl alcohol 20mL, catalytic component HBr 6mmol are added in vial；
S2, by the above-mentioned solid-liquid body for mixing under 30 DEG C of temperature conditionss ultrasound 3min, supersonic frequency is 30kHz, turbid solution is changed into light green from yellow；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid is cleaned with methanol solvate 3 times, i.e. available (NH=CHNH after drying3)4SbBr6Green powder, material sends green glow under 365nm ultra violet lamps, uses The fluorescence emission wavelengths of sepectrophotofluorometer test material are 528nm.
(the NH=CHNH of embodiment 103)4GeBr6The preparation of perovskite luminescent material
S1, by perovskite component NH=CHNH3GeBr31mmol, organic amine halogen component NH=CHNH3Br 2.8mmol, Organic solvent constituent methyl alcohol 20mL, catalytic component HBr are added in vial；
S2, by the above-mentioned solid-liquid body for mixing under 60 DEG C of temperature conditionss ultrasound 6min, supersonic frequency is 30kHz, turbid solution is changed into white from filbert；
S3, above-mentioned white opacity liquid is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid cleans 3 with methanol solvate It is secondary, i.e. available (NH=CHNH after drying3)4GeBr6Powder, material sends faint green glow under 365nm ultra violet lamps, uses The fluorescence emission wavelengths of sepectrophotofluorometer test material are 518nm.
Prepare inorganic perovskite crystallite luminescent material
Embodiment 11Cs4PbBr6The preparation of perovskite luminescent material
S1, by metal halide component PbBr21mmol, halogenation cesium component CsBr 3.6mmol, organic solvent constituent DMF (dimethylformamide) 15mL is added in vial；
S2, by the above-mentioned solid-liquid body for mixing ultrasonic disperse 25min under 25 DEG C of temperature conditionss, supersonic frequency is 25kHz, turbid solution is changed into light green from yellow；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid cleans 3 with DMF solvent It is secondary, can obtain Cs after drying4PbBr6Green powder, material sends very strong green glow under 365nm ultra violet lamps, and Fig. 4 is Cs4PbBr6The microcosmic collection of illustrative plates of perovskite luminescent material；As shown in Figures 5 and 6, sepectrophotofluorometer test result shows Cs4PbBr6The emission wavelength of perovskite luminescent material is 516nm, and a width of 19nm of half-peak, quantum yield test result shows Cs4PbBr6The absolute fluorescence quantum yield of perovskite luminescent material is 90%.Fig. 7 is the Cs for obtaining4PbBr6Perovskite lights material The structural representation of material.
Embodiment 12Cs4PbBr6The preparation of perovskite luminescent material
S1, by metal halide component PbBr210mmol, halogenation cesium component CsBr 38mmol, organic solvent constituent DMAC (dimethylacetylamide) 50mL is placed in the rustless steel container of ball mill；
S2, the steel ball for adding diameter 30mm, proceed by grinding under 25 DEG C of temperature conditionss, continue 60min, cylinder Rotating speed is 40r/min；
The yellowish mixture of colours solid-liquid that S3, grinding are obtained removes a layer solid, is cleaned with DMAC solvents 3 times, after drying Obtain Cs4PbBr6Green powder, quality is 105g after weighing, and material sends very strong green glow under 365nm ultra violet lamps, glimmering Light spectrophotometer test result shows Cs4PbBr6The emission wavelength of perovskite luminescent material is 525nm, a width of 20nm of half-peak.
Embodiment 13Cs4SnBr6The preparation of perovskite luminescent material
S1, by metal halide component SnBr21mmol, halogenation cesium component CsBr 4mmol, organic solvent constituent DMF 20mL, catalytic component HBr 0.25mmol are added in vial；
S2, the solid-liquid body that will be mixed ultrasonic disperse 10min under 70 DEG C of temperature conditionss, turbid solution are become by yellow It is light green；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid cleans 3 with DMF solvent It is secondary, can obtain Cs after drying4SnBr6Pale green powder.Material sends green-yellow light, fluorescence spectrophotometer under 365nm ultra violet lamps Photometer test result shows Cs4SnBr6The emission wavelength of perovskite luminescent material is 555nm, a width of 35nm of half-peak.
Embodiment 14Cs4GeBr6The preparation of perovskite luminescent material
S1, by metal halide component GeBr21mmol, halogenation cesium component CsBr 4mmol, organic solvent constituent DMF 20mL is added in vial；
S2, the solid-liquid body that will be mixed ultrasonic disperse 50min under 90 DEG C of temperature conditionss, turbid solution are become by yellow For faint yellow；
S3, above-mentioned faint yellow turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid cleans 3 with DMF solvent It is secondary, can obtain Cs after drying4GeBr6Pale yellow powder.Material sends gold-tinted, fluorescence spectrophotometer light under 365nm ultra violet lamps Degree measurement test result shows Cs4GeBr6The emission wavelength of perovskite luminescent material is 545nm, a width of 34nm of half-peak.
Embodiment 15Cs4SbBr6The preparation of perovskite luminescent material
S1, by metal halide component SbBr21mmol, halogenation cesium component CsBr 4mmol, organic solvent constituent DMF 20mL is added in vial；
S2, the solid-liquid body that will be mixed ultrasonic disperse 40min under 30 DEG C of temperature conditionss, turbid solution are become by yellow It is light green；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid cleans 3 with DMF solvent It is secondary, can obtain Cs after drying4SbBr6Pale green powder.Material sends green glow, fluorescence spectrophotometer light under 365nm ultra violet lamps Degree measurement test result shows Cs4SbBr6The emission wavelength of perovskite luminescent material is 527nm, a width of 31nm of half-peak.
Embodiment 16Cs4CuBr6The preparation of perovskite luminescent material
S1, by metal halide component CsCuBr31mmol, halogenation cesium component CsBr2.8mmol, organic solvent constituent DMF 20mL, catalytic component KBr 0.2mmol are added in vial；
S2, the solid-liquid body that will be mixed ultrasonic disperse 10min under 30 DEG C of temperature conditionss, turbid solution is by yellow green It is changed into filbert；
S3, above-mentioned light green turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid cleans 3 with DMF solvent It is secondary, can obtain Cs after drying4CuBr6Brown powder.Material sends micro- gold-tinted, fluorescence spectrophotometer under 365nm ultra violet lamps Photometer test result shows Cs4CuBr6The emission wavelength of perovskite luminescent material is 553nm, a width of 43nm of half-peak.
Embodiment 17Cs4MnBr6The preparation of perovskite luminescent material
S1, by metal halide component MnBr21mmol, halogenation cesium component CsBr 4mmol, organic solvent constituent DMF 20mL is added in vial；
S2, the solid-liquid body that will be mixed ultrasonic disperse 45min under 50 DEG C of temperature conditionss, turbid solution is by filbert It is changed into faint yellow；
S3, above-mentioned faint yellow turbid solution is carried out into centrifugal treating, give up supernatant liquid, lower floor's solid cleans 3 with DMF solvent It is secondary, can obtain Cs after drying4MnBr6Brown powder.Material sends green-yellow light, fluorescence spectrophotometer under 365nm ultra violet lamps Photometer test result shows Cs4MnBr6The emission wavelength of perovskite luminescent material is 545nm, a width of 38nm of half-peak.
Embodiment 18 is based on (NH=CHNH3)4PbBr6The photo luminescent devices and its backlight of perovskite crystallite luminescent material It is prepared by source
By (NH=CHNH3)4PbBr6Perovskite luminescent material 0.1g, KSF fluorination matter fluorescent powder 0.1g, 1:1 is well mixed OE6551A and OE6551B silica gel 0.5g be placed in small beaker, well mixed to obtain the glue containing luminescent material, deaeration is treated With；
By on the patch-type LED of the above-mentioned glue package for mixing to 0.5W, heat cure 30min is carried out at 100 DEG C, Solidify afterwards 2h at 120 DEG C, you can obtain luminescence generated by light LED component, the chromaticity coordinates of test gained LED is (0.29,0.31), colour temperature It is 8400K；
Above-mentioned photo luminescent devices are welded on 55 inches of liquid crystal display lamp bar support, side entering type is then attached to Backlight module in, obtained 55 inch liquid crystal display device white light backlights, the colour gamut of test gained backlight is NTSC colors 1.21 times of domain standard.
Embodiment 19 is based on (NH=CHNH3)4PbBr6It is prepared by the backlight of LCD of perovskite luminescent material
By (NH=CHNH3)4PbBr6Perovskite luminescent material 10g, KSF fluorination matter fluorescent powder 10g, uv-curable glue 80g It is placed in small beaker, well mixed to obtain the glue containing luminescent material, deaeration is stand-by；
By the above-mentioned glue for mixing by casting machine, it is coated uniformly in transparent PET substrate, in the uviol lamp of 320nm Solidification 45min is carried out under irradiation, (NH=CHNH is based on3)4PbBr6The optical thin film of perovskite luminescent material；
Optical thin film is placed in the surface of 65 inch backlight module light guide plates, and ethereal blue light is fixed in backlight module side Lamp bar, the launch wavelength of blue light lamp bar is 454nm, and 65 inches of liquid crystal display white light backlight is obtained after being fixed with frame Source, backlight spectra are as shown in figure 8, test result shows that the chromaticity coordinates of the white light backlight for assembling is (0.27,0.28), colour temperature It is 11000K, colour gamut is 1.22 times of NTSC standard.
Finally it should be noted that：Above-described each embodiment is merely to illustrate technical scheme, rather than to it Limitation；Although being described in detail to the present invention with reference to the foregoing embodiments, it will be understood by those within the art that： It can still modify to the technical scheme described in previous embodiment, or which part or all technical characteristic are entered Row equivalent；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technical side The scope of case.

Claims (15)

1. a kind of hydridization perovskite crystallite luminescent material, it is characterised in that：The formula of the hydridization perovskite crystallite luminescent material It is A4BX6, wherein A is CH3NH3 +, NH=CHNH3 +、C(NH2)3 +Or R2NH3 +In any one, B be Ge, Sn, Pb, Sb, Bi, Any one in the metal ion of Cu or Mn, X is Cl-、Br-And I-In at least one, wherein R2For chain carbon atom number exists Straight chain saturated alkyl group or saturation branched alkyl group or unsaturated linear alkyl groups or unsaturated side chain alkane between 1-8 Base group or aromatic group.
2. a kind of method of the hydridization perovskite crystallite luminescent material prepared described in claim 1, it is characterised in that：It include with Lower step：
S1, perovskite component, organic solvent constituent and catalytic component are respectively added in glass container, be well mixed To the question response material of solid-liquid two-phase coexistent, the ratio of perovskite component and organic solvent constituent is 1:(1-25) mol/L, catalyst The ratio (0.2-0.5) of component and organic solvent constituent:1mol/L, the perovskite component is by that can be dissolved completely in organic solvent group Point in the first perovskite component and be incompletely dissolved in organic solvent constituent the second perovskite component constitute；
S2, the question response material that will be obtained in step S1 are in stirring reaction condition, friction reaction condition, ultrasonic reaction condition, shake Swing and reacted under the one or more of which reaction condition in reaction condition or heating response condition, the reaction time is 1- 60min, obtains solid material after reaction；
S3, the solid material that will be obtained in step S2, are carried out using with organic solvent constituent identical organic solvent in step S1 Repeated washing, drying, finally obtain hydridization perovskite crystallite luminescent material.
3. it is according to claim 2 prepare hydridization perovskite crystallite luminescent material method, it is characterised in that：In step S1 The first perovskite component is that formula is ABX3Perovskite material or formula be BXnMetal halide, the second calcium titanium Ore deposit component is that formula is the halide of AX.
4. it is according to claim 3 prepare hydridization perovskite crystallite luminescent material method, it is characterised in that：Wherein A is CH3NH3 +, NH=CHNH3 +、C(NH2)3 +Or R2NH3 +In any one, B for Ge, Sn, Pb, Sb, Bi, Cu or Mn metal from Any one in son, X is Cl-、Br-And I-In at least one, R2It is saturated straight chain of the chain carbon atom number between 1-8 Alkyl group or saturation branched alkyl group or unsaturated linear alkyl groups or unsaturated side chain alkyl group or aromatic group.
5. it is according to claim 2 prepare hydridization perovskite crystallite luminescent material method, it is characterised in that：In step S1 Organic solvent constituent is selected from acetonitrile, acetone, methyl ethyl ketone, 2- amylalcohols, 3- amylalcohols, propionitrile, the tert-butyl alcohol, ethylenediamine, 1,2- Dichloroethanes, butanone, tert-pentyl alcohol, 2 pentanone, isoamyl ketone, dichloromethane, pyridine, methyl acetate, 4-methyl-2 pentanone, 3- penta At least one in ketone, ethyl acetate and diethyl carbonate.
6. it is according to claim 5 prepare hydridization perovskite crystallite luminescent material method, it is characterised in that：In step S1 Organic solvent constituent is selected from least one in acetone, acetonitrile, methyl ethyl ketone, propionitrile, ethyl acetate.
7. it is according to claim 2 prepare hydridization perovskite crystallite luminescent material method, it is characterised in that：In step S1 Catalytic component is that, selected from least one in halogen acids HX, sodium halide NaX or potassium halide KX, X is Cl-、Br-Or I-。
8. it is according to claim 3 prepare hydridization perovskite crystallite luminescent material method, it is characterised in that：The formula It is ABX3Perovskite material and formula for the mol ratio of the halide of AX be 1：(2-3), the formula is BXnMetal halide Thing is with formula for the mol ratio of the halide of AX is 1:(3-4).
9. it is according to claim 2 prepare hydridization perovskite crystallite luminescent material method, it is characterised in that：In step S2 Stirring reaction condition be magnetic agitation, mechanical agitation or disperse at a high speed that the wherein reaction time is 1-60min, and mixing speed is 50-5000r/min；
Friction reaction condition is mechanical attrition method, and the wherein reaction time is 1-60min, and drum speed is 20-40r/min, steel ball A diameter of 20-60mm；
The reaction time of ultrasonic reaction condition is 1-60min, and supersonic frequency is 20-40kHz, and power density is 0.3-1W/cm2；
Concussion reaction condition is shaken for water bath with thermostatic control, and the wherein reaction time is 1-60min, and frequency of oscillation is 100-300 times/min, Amplitude is 20-30mm, and bath temperature is 30-85 DEG C；And
The reaction time of heating response condition is 1-60min, and temperature range is 20-90 DEG C；
The question response material that will be obtained in step S1 in step S2 is in stirring reaction condition, friction reaction condition, ultrasonic reaction bar Reacted under two of which reaction condition in part, concussion reaction condition or heating response condition.
10. a kind of photo luminescent devices, it is characterised in that：The photo luminescent devices contain the hydridization calcium described in claim 1 Titanium ore crystallite luminescent material.
A kind of 11. LCD backlight sources, it is characterised in that：The LCD backlight source includes the light described in claim 10 Electroluminescence device.
A kind of 12. preparation methods of inorganic perovskite crystallite luminescent material, it is characterised in that：It is comprised the following steps：
S1, perovskite component, organic solvent constituent and catalytic component are respectively added in glass container, be well mixed To the question response material of solid-liquid two-phase coexistent, the ratio of perovskite component and organic solvent constituent is 1:(1-25) mol/L, catalyst The ratio (0.2-0.5) of component and organic solvent constituent:1mol/L, the perovskite component is by that can be dissolved completely in organic solvent group Point in the first perovskite component and be incompletely dissolved in organic solvent constituent the second perovskite component constitute；
S2, the question response material that will be obtained in step S1 are in stirring reaction condition, friction reaction condition, ultrasonic reaction condition, shake Swing and reacted under the one or more of which reaction condition in reaction condition or heating response condition, the reaction time is 1- 60min, obtains solid material after reaction；
S3, the solid material that will be obtained in step S2, are repeated using with organic solvent constituent identical organic solvent in S1 Wash, dry, finally obtain hydridization perovskite crystallite luminescent material.
The preparation method of 13. inorganic perovskite crystallite luminescent materials according to claim 12, it is characterised in that：Step S1 In the first perovskite component be formula be MBX3Perovskite material or formula be BXnMetal halide, second perovskite Component is that formula is the halide of MX；
Organic solvent constituent is dimethylformamide or dimethylacetylamide in S1；
Catalytic component is at least one in halogen acids HX, sodium halide NaX or potassium halide KX in S1, and X is Cl-、Br-Or I-。
The preparation method of 14. inorganic perovskite crystallite luminescent materials according to claim 13, it is characterised in that：Wherein M It is Cs+、Ru+Or K+In any one, B for Ge, Sn, Pb, Sb, Bi, Cu or Mn metal ion in any one, X is Cl-、Br-And I-In at least one, R2The straight chain saturated alkyl group or saturation side chain that are chain carbon atom number between 1-8 Alkyl group or unsaturated linear alkyl groups or unsaturated side chain alkyl group or aromatic group.
The preparation method of 15. inorganic perovskite crystallite luminescent materials according to claim 12, it is characterised in that：Step S2 In stirring reaction condition for magnetic agitation, mechanical agitation or at a high speed disperse, wherein the reaction time be 1-60min, mixing speed It is 50-5000r/min；
Friction reaction condition is mechanical attrition method, and the wherein reaction time is 1-60min, and drum speed is 20-40r/min, steel ball A diameter of 20-60mm；
The reaction time of ultrasonic reaction condition is 1-60min, and supersonic frequency is 20-40kHz, and power density is 0.3-1W/cm2；
Concussion reaction condition is shaken for water bath with thermostatic control, and the wherein reaction time is 1-60min, and frequency of oscillation is 100-300 times/min, Amplitude is 20-30mm, and bath temperature is 30-85 DEG C；And
The reaction time of heating response condition is 1-60min, and temperature range is 20-90 DEG C.
The question response material that will be obtained in step S1 in step S2 is in stirring reaction condition, friction reaction condition, ultrasonic reaction bar Reacted under two of which reaction condition in part, concussion reaction condition or heating response condition.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104327827A (en) * 2014-11-03 2015-02-04 南昌航空大学 Preparation of perovskite quantum dot nanocrystals and application of perovskite quantum dot nanocrystals in quantum dot solar cells
CN105647530A (en) * 2016-02-01 2016-06-08 南京理工大学 Preparation method of metal halide inorganic perovskite quantum dots
CN106938855A (en) * 2017-04-06 2017-07-11 合肥工业大学 A kind of method that scale quickly prepares perovskite semi-conducting material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104327827A (en) * 2014-11-03 2015-02-04 南昌航空大学 Preparation of perovskite quantum dot nanocrystals and application of perovskite quantum dot nanocrystals in quantum dot solar cells
CN105647530A (en) * 2016-02-01 2016-06-08 南京理工大学 Preparation method of metal halide inorganic perovskite quantum dots
CN106938855A (en) * 2017-04-06 2017-07-11 合肥工业大学 A kind of method that scale quickly prepares perovskite semi-conducting material

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
ABDELRAHMAN M. ASKAR 等: "Multinuclear Magnetic Resonance Tracking of Hydro, Thermal, and Hydrothermal Decomposition of CH3NH3PbI3", 《J. PHYS. CHEM. C》 *
BEVERLYR . VINCENT等: "Alkylammonium lead halides. Part 1. Isolated PbI64- ions in (CH3NH3)4PbI6.2H2O", 《CAN.J.CHEM.》 *
CHRIS GUHRENZ 等: "Solid-State Anion Exchange Reactions for Color Tuning of CsPbX3 Perovskite Nanocrystals", 《CHEM. MATER.》 *
GIACOMO GIORGI 等: "Structural and electronic features of small hybrid organic–inorganic halide perovskite clusters: a theoretical analysis", 《PHYS.CHEM.CHEM.PHYS.》 *
JI-HYUN CHA等: "Photoresponse of CsPbBr3 and Cs4PbBr6 Perovskite Single Crystals", 《J. PHYS. CHEM. LETT.》 *
JIN HUANG等: "Hydrobromic acid assisted crystallization of MAPbI3-xClx for enhanced power conversion efficiency in perovskite solar cells", 《RSC ADV.》 *
MAKHSUD I. SAIDAMINOV等: "Pure Cs4PbBr6:Highly Luminescent Zero-Dimensional Perovskite Solids", 《ACS ENERGY LETT.》 *
MYKHAILO SYTNYK 等: "Quasi-epitaxial Metal-Halide Perovskite Ligand Shells on PbS Nanocrystals", 《ACS NANO》 *
YUKO TAKEOKA等: "Hydrothermal Synthesis and Structure of Zero-dimensional Organic–inorganic Perovskites", 《CHEMISTRY LETTERS》 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN110869466B (en) * 2017-07-11 2023-04-28 南洋理工大学 Low-dimensional inorganic/organic hybrid metal halide perovskite
CN110869466A (en) * 2017-07-11 2020-03-06 南洋理工大学 Low-dimensional inorganic/organic hybrid metal halide perovskites
WO2019013709A1 (en) * 2017-07-11 2019-01-17 Nanyang Technological University Low-dimensional inorganic-organic hybrid metal halide perovskites
CN108011292A (en) * 2017-10-27 2018-05-08 北京理工大学 Colloidal Quantum Dots continuous wave laser and preparation method thereof
CN109956874A (en) * 2017-12-26 2019-07-02 致晶科技（北京）有限公司 A kind of perovskite material and its preparation method and application
WO2019128995A1 (en) * 2017-12-26 2019-07-04 北京理工大学 Ammonium salt, perovskite material, and application
CN109956874B (en) * 2017-12-26 2020-08-11 致晶科技（北京）有限公司 Perovskite material and preparation method and application thereof
CN110391338A (en) * 2018-04-19 2019-10-29 中国科学院大连化学物理研究所 A kind of two dimension germanium tin mixing perovskite material and synthesis and application
CN108531172A (en) * 2018-05-21 2018-09-14 北京理工大学 A kind of preparation method and applications of hydridization perovskite crystallite luminescent material
CN108531172B (en) * 2018-05-21 2020-09-04 北京理工大学 Preparation method and application of hybrid perovskite microcrystalline luminescent material
CN109095784A (en) * 2018-07-25 2018-12-28 许昌学院 A kind of chemical method of large area preparation halogenation first ammonia bismuth semiconductor optoelectronic thin-film material
CN111364103A (en) * 2018-12-25 2020-07-03 北京理工大学 Perovskite single crystal material, preparation method and application thereof
CN109777403A (en) * 2019-03-14 2019-05-21 吉林大学 A kind of high fluorescence efficiency Cs2AgxNa1-xInCl6The preparation method of Double Perovskite
CN111233031A (en) * 2020-01-19 2020-06-05 国家纳米科学中心 Perovskite quantum dot and preparation method thereof
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CN113636588A (en) * 2020-04-27 2021-11-12 南京大学 Cs4PbBr6Nanocrystalline of analogue thereof and preparation method
CN113636588B (en) * 2020-04-27 2022-10-14 南京大学 Cs 4 PbBr 6 Nanocrystalline of analogue thereof and preparation method
CN111944525B (en) * 2020-08-25 2022-05-10 深圳大学 Zero-dimensional cesium-lead-bromine inorganic perovskite material and preparation method thereof
CN111944525A (en) * 2020-08-25 2020-11-17 深圳大学 Zero-dimensional cesium-lead-bromine inorganic perovskite material and preparation method thereof
CN113046063A (en) * 2021-03-23 2021-06-29 广东工业大学 Hybrid perovskite luminescent material and preparation method and application thereof
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CN113388394A (en) * 2021-06-08 2021-09-14 厦门大学 Photoluminescent material, application thereof, stressed tracer material and ballistic gel

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