CN108531172A - A kind of preparation method and applications of hydridization perovskite crystallite luminescent material - Google Patents
A kind of preparation method and applications of hydridization perovskite crystallite luminescent material Download PDFInfo
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Abstract
This application discloses a kind of perovskite micro crystal material, the hydridization perovskite micro crystal material includes chemical formula perovskite shown in formula I and the chemical formula perovskite as shown in Formula II;AM2X5Formulas I;A4MX6Formula II;In perovskite insertion perovskite as shown in Formula II shown in formula I;Wherein, A is selected from CH3NH3 +, NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;R2Selected from hydrogen, C1~C10Alkyl, C1~C10Unsaturated alkyl;M is metal ion, and the metal is selected from least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl, Ag;X is selected from least one of halide anion.The perovskite micro crystal material luminous efficiency is high, stability is good.
Description
Technical field
This application involves a kind of preparation method and applications of hydridization perovskite crystallite luminescent material, belong to material and its system
Standby field.
Background technology
The perovskite material reported at present is mainly ABX3The perovskite material of structure, some less are about A4BX6Structure
Perovskite material, however it is reported that not about AB2X5The relevant report of the perovskite material of structure.
Up to the present, quanta point material mainly has a typical II-VI group CdSe quantum dot in the application of display field
The CuInS quantum dot systems etc. of system, the InP quantum dots system of iii-v or I-III-VI race.
In recent years, metal halide ABX3The appearance of type perovskite material further improves people and prepares half to solwution method
Conductor is nanocrystalline or the related of quanta point material recognizes.Occur a new class of perovskite again in nearest research report to shine
Material (chemical formula Cs4PbBr6), this kind of material has and ABX3The excellent optical property that type perovskite quantum dot is mutually equal to, tool
There is huge application potential.It is this kind of to be referred to as the half of zero dimension perovskite in particular with the optimization and improvement of material preparation method
Conductor material is shown and ABX3The different special photoelectric property of type perovskite (such as photoluminescence intensity height, exciton knot
Closing can be big).These new characteristics make Cs4PbBr6In such as light emitting diode, electroluminescent device, laser and Photoelectric Detection
Application in device is in unprecedented position.
However, existing inorganic A4BX6The preparation method of type perovskite luminescent material is mostly comparatively laborious, and can introduce
The organic molecules such as oleic acid (OA), oleyl amine (OLA) are unfavorable for the cleaning and purification of later stage quantum dot.
Invention content
According to the one side of the application, a kind of hydridization perovskite micro crystal material is provided, the present invention prepares for the first time
AB2X5Type is embedded in A4MX6The hydridization perovskite micro crystal material of type, the hydridization perovskite micro crystal material luminous efficiency height, stability
It is good.
The hydridization perovskite micro crystal material includes chemical formula perovskite shown in formula I and chemical formula as shown in Formula II
Perovskite;
AM2X5Formulas I;
A4MX6Formula II;
In perovskite insertion perovskite as shown in Formula II shown in formula I;
Wherein, A is selected from CH3NH3 +, NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;
R2Selected from hydrogen, C1~C10Alkyl, C1~C10Unsaturated alkyl;
M is metal ion, and the metal is selected from least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl, Ag;
X is selected from least one of halide anion.
Optionally, R2The straight chain saturated alkyl group for being chain carbon atom number between 1-8 or saturation branched alkyl group or
Unsaturated linear alkyl groups or unsaturated side chain alkyl group or aromatic group.
Optionally, wherein R2Selected from hydrogen, C1~C4Alkyl;
X is selected from Cl-、Br-、I-At least one of.
Optionally, the scale of the hydridization perovskite micro crystal material is 0.001mm~200mm.
Optionally, the size of the hydridization perovskite micro crystal material is 101~104mm3。
Optionally, wherein R2Selected from methyl, ethyl, propyl, isopropyl, butyl or tertiary butyl.
Optionally, A is selected from CH3NH3 +, NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Cs+In one kind.
Optionally, the emission wavelength of the hydridization perovskite micro crystal material is 300nm~1000nm.
Optionally, the emission wavelength of the hydridization perovskite micro crystal material is 490nm~520nm.
Optionally, the fluorescence quantum yield of the hydridization perovskite micro crystal material reaches 80% or more.
Optionally, the fluorescence quantum yield of the hydridization perovskite micro crystal material reaches 90% or more.
Specifically, the present invention provides a kind of hydridization perovskite crystallite luminescent material, and the hydridization perovskite crystallite shines material
The general formula of material is AB2X5, wherein A is CH3NH3 +, NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+In one kind,
B is any one in the metal ion of Ge, Sn, Pb, Sb, Bi, Cu or Mn, X Cl-、Br-And I-At least one of.Its
Middle R2The straight chain saturated alkyl group for being chain carbon atom number between 1-8 or saturation branched alkyl group or unsaturated straight chained alkyl
Group or unsaturated side chain alkyl group or aromatic group.The present invention has prepared AB for the first time2X5The luminous material of the inorganic perovskite of type
Material, the inorganic perovskite luminescent material luminous efficiency is high, stability is good.
According to further aspect of the application, a kind of method preparing the hydridization perovskite micro crystal material, institute are provided
State that method is simple, versatile, the yield of material is high, can reach 80% or more, emission wavelength can between 300nm~1000nm
It adjusts, impurity is few, and cleaning purification is easy, is at low cost, and material purity is high.
The preparation method of the hydridization perovskite micro crystal material, at least includes the following steps:
S1) additive is added in the solution containing perovskite presoma, obtains solid-liquid two-phase mixtures system I;
S2) by step S1) described in solid-liquid two-phase mixtures system I reaction, obtain perovskite micro crystal material.
Optionally, step S1) described in additive be selected from R31-COOH、R32-OH、R33-SH、R34In-C=S at least
It is a kind of;
Wherein, R31、R32、R33、R34Independently selected from C1~C18Alkyl, C1~C18Unsaturated alkyl.
Optionally, step S1) described in additive it is at least a kind of in ethyl alcohol, oleic acid.
Optionally, step S1) described in perovskite presoma include organic ammonium salt AX1With metal salt MX2;
Wherein, the A is selected from CH3NH3 +, NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+In at least
It is a kind of;
M is metal ion, and the metal is selected from least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl, Ag;
The X1、X2Independently selected from least one of halide anion.
Optionally, the organic ammonium salt AX1With metal salt MX2Molar ratio be 1:1~10.
Optionally, the organic ammonium salt AX1With metal salt MX2Molar ratio be 1:3.5~4.5.
Optionally, the organic ammonium salt AX1And the ratio of additive is 1:(1~100) mol/ μ L.
Optionally, the organic ammonium salt AX1And the ratio of additive is 1:(1~64) mol/ μ L.
Optionally, step S1) described in the solvent of solution be selected from least one of DMF, HBr, DMSO.
Optionally, the organic ammonium salt AX1And the ratio of solvent is 1:(2~10) mol/L.
Optionally, the organic ammonium salt AX1And the ratio upper limit of additive is selected from 1:8mol/ μ L or 1:64mol/μL;Lower limit
Selected from 1:1mol/ μ L or 1:8mol/μL.
Optionally, step S1) in solvent be DMF and HBr volume ratios be 1:The mixed solvent of (0.1~10).
Optionally, step S2) described in the condition reacted in stirring, friction, ultrasound, concussion, heating at least one
Kind.
Optionally, it is described be stirred to react condition be magnetic agitation, mechanical agitation or high speed dispersion, the reaction time be 30~
120 minutes, mixing speed was 80~100r/min;
The friction reaction condition is mechanical attrition method, and the reaction time is 30~120 minutes, drum speed 23.8r/
Min, steel ball size 100mm;
The ultrasonic reaction condition is that ultrasonic time is 30~120 minutes, and supersonic frequency is 40~60KHz, and power is
100W;
The concussion reaction condition be water bath with thermostatic control concussion, the reaction time be 30~120 minutes, concussion frequency be 80~
100 times/min, amplitude 40mm, bath temperature is 50~80 DEG C;
The heating reaction condition be 20~60 minutes in the reaction time, be heated to 80~120 DEG C.
Optionally, step S2) it includes at least:By S1) obtained mixed system I dissolves by heating, obtain solution II;By solution
II is kept for 20~40 minutes at 80~120 DEG C, then continuously decreases temperature to seeded growth after 60~10 DEG C, 2~4 days, 25~
It can be obtained the hydridization perovskite micro crystal material after 35 days.
Optionally, step S2) described in the rate that cools down be 5~15 DEG C/h.
Optionally, step S2) described in the rate that cools down be 10 DEG C/h.
Optionally, step S2) in by S1) obtained mixed system I heating water baths dissolve to 80~100 DEG C.
Optionally, step S2) in obtained hydridization perovskite crystal washed through butyrolactone and toluene.
As a kind of specific embodiment, the preparation method of the hydridization perovskite micro crystal material includes at least following
Step:
Additive is added in the solution containing perovskite presoma, water-bath is allowed to whole dissolvings, gradually cools down, growth
Seed crystal cleans, and filtering obtains hydridization perovskite micro crystal material.
Optionally, hybrid inorganic perovskite luminescent material CsPb is prepared using the preparation method of the present invention2Br5, method letter
Single, versatile, the yield of material is high, can reach that 90% or more, impurity is few, and cleaning purification is easy, is cost-effective, after cleaning
CsPb2Br5Material component purity is high (purity close to 100%), is easy to carry out technique amplification, is easy for having been realized at present
The preparation of hectogram rank.
Specifically, the organic solvent constituent that the preparation method of the application uses matches with perovskite component, the calcium of selection
Titanium ore component one of which, which can be completely dissolved, to be dispersed in organic solvent constituent, another cannot then dissolve dispersion well
In organic component, exist in the form of solid phase, to form solid-liquid two-phase coexistent body, the solid-liquid two-phase mixture of formation is by stirring
Mix, rub, ultrasound, the control of shaking or heat these conditions start to react, disperse one of which calcium titanium in organic solvent
Mine component comes into full contact with another perovskite component of solid phase reacts, and this special solid-liquid contact reaction system ensure that calcium titanium
Mine component reaction is to AB2X5Type thaumatropy.Avoid reaction system perovskite component in existing technology during the reaction
It has greatly to ABX3Type structure turns.
Specifically, the present invention is mainly A4BX6The basis of type perovskite micro crystal material original preparation method is to add some to have
Machine additive such as R-COOH, R-OH, R-SH, R-C=S etc. obtain novel perovskite material, and wherein R is that chain carbon atom number exists
Straight chain saturated alkyl group or saturation branched alkyl group or unsaturated linear alkyl groups between 1-18 or unsaturated side chain
Alkyl group or aromatic group.The present invention has prepared AB for the first time2X5The inorganic perovskite luminescent material of type, prepared is inorganic
Perovskite luminescent material luminous efficiency is high, stability is good.AB is prepared the present invention also provides a kind of2X5Perovskite crystallite luminescent material
Method, this method is simple, versatile, and the yield of material is high, can reach 90% or more, emission wavelength is in 490nm~520nm
Between it is adjustable, impurity is few, and cleaning purification is easy, is at low cost, and material purity is high.
According to the another aspect of the application, a kind of luminescent material is provided, including the hydridization perovskite micro crystal material, described
At least one of the hydridization perovskite micro crystal material that is prepared of method.
The condition of related to numberical range can be independently selected from the arbitrary point value in the numberical range in the application.
" C in the application1~C18”、“C1~C10" etc. refer both to the carbon atom number that group is included.
In the application, " alkyl " is to be formed by group by losing any one hydrogen atom on alkane compound molecule.
In the application, " alkyl " is that the group formed after a hydrogen atom on carbon atom is lost in hydrocarbon molecule.The hydrocarbon
For carbohydrate, such as alkane, alkene, alkynes are hydrocarbon.
In the application, " aryl " is to lose to be formed after any one hydrogen atom on aromatic rings in aromatic compound molecule
Group.
The advantageous effect that the application can generate includes:
1) present invention has prepared AM for the first time2X5Inorganic perovskite crystallite luminescent material of type and preparation method thereof, it is prepared
Crystallite perovskite luminescent material AM2X5Purity can reach 90% or more, and luminous efficiency is high, and fluorescence quantum yield can reach
80% or more, stability is good, as shown in Figure 4.Prepared crystallite perovskite material carries out fluorometric investigation, test result such as Fig. 3
It is shown, the portable ultraviolet detection light irradiations of ZF-7A are used in dark conditions, and the sparkling crystal of green is presented.
2) inorganic perovskite luminescent material CsPb is prepared using the preparation method of the present invention2Br5, method is simple, versatility
By force, the yield of material is high, and it is few to reach 90% or more, impurity, and cleaning purification is easy, cost-effective, the CsPb after cleaning2Br5Material
Expect that compositional purity is high (purity close to 100%), is easy to carry out technique amplification, is easy for having been realized in hectogram rank at present
It prepares.
3) organic solvent constituent that the method for the present invention uses matches with perovskite component, and the perovskite component of selection is wherein
One kind can be completely dissolved and be dispersed in organic solvent constituent, another cannot then be dissolved well is dispersed in organic component
In, exist in the form of solid phase, to form solid-liquid two-phase coexistent body, the solid-liquid two-phase mixture of formation by stirring, friction, surpass
Sound, concussion heat the control of these conditions and start to react, disperse one of which perovskite component in organic solvent with it is solid
Another perovskite component of phase comes into full contact with reaction, and this special solid-liquid contact reaction system ensure that perovskite component reaction
To AM2X5Type thaumatropy.Avoid the reaction system perovskite component in existing technology have during the reaction it is very big by one
Partly to AMX3Type structure turns.
4) the method for the present invention introduces additive simultaneously in the preparation, can be effectively in original A4MX6It is prepared by perovskite material
On the basis of obtain new A M2X5Type perovskite crystallite luminescent material, the material is compared to A4MX6Type perovskite material has more
Big Wavelength tunable adjusting range (490nm~520nm).
Description of the drawings
Fig. 1 is sample 1#With 2#XRD diagram.
Fig. 2 is sample 3#With 4#XRD diagram.
(a) and (b) figure after ultraviolet irradiation before the ultraviolet irradiation for the sample that Fig. 3 is prepared for the application.
Fig. 4 is sample 2#Fluorogram.
Specific implementation mode
The application is described in detail with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and solvent are bought by commercial sources.
Analysis method is as follows in embodiments herein:
XRD tests are carried out using Bruker/D8FOCUS X-ray diffraction instrument, test condition is CuKr radiation sources, wavelength
1.5405 angstroms, 60 degree are swept to since 5 degree with 3 degree every point.
Spectrofluorimetry is carried out using the F-380 fluophotometers of Tianjin Gangdong development in science and technology Co., Ltd production.
Embodiment 1 prepares perovskite material CsPb2Br5Sample 1#
(1)1mol PbBr2, 4mol CsBr and 8 μ L oleic acid additives, be dissolved in 1.1mL DMF and HBr at room temperature
(volume ratio 1:0.8) in fixation mixture.
(2) temperature that mixture is controlled using external water-bath is allowed to be completely dissolved, and bath temperature control is completely molten at 100 DEG C
It is kept for 30 minutes after solution, continuously decreases temperature to 10 DEG C, rate of temperature fall is 10 DEG C/h.
Seed crystal is slowly grown after (3) 3 days, and shape is cube (1 × 1 × 0.2mm3).After one month, CsPb2Br5It receives
Meter Jing Ti is successfully embedded in Cs4PbBr6In crystal, it is planted in drag, with ultra violet lamp, the sparkling of green is presented
Crystal is cleaned and is filtered with butyrolactone and toluene later.
Gained sample is 1#。
Embodiment 2 prepares perovskite material Cs4PbBr6Sample 2#~4#
Preparation process is with embodiment 1, the difference is that sample 2#~4#It is separately added into 64 μ L oleic acid additives, 8 μ L ethyl alcohol
Additive and 64 μ L ethanol additives.
Embodiment 3 prepares perovskite material sample 5#~10#
Preparation process see the table below with embodiment 1, raw material and reaction condition.
Table 1
4 perovskite material sample 1 of embodiment#~10#Structural characterization
Structural analysis is carried out to the perovskite material obtained in embodiment 1 to embodiment 3, tests XRD spectra.Typically such as
Fig. 1 counter samples 1#~2#With Fig. 2 counter samples 3#~4#Shown in calcium titanium material.It can be seen from the figure that successfully being made in embodiment
It is standby to have obtained AM2X5Embedded A4MX6Obtain hydridization perovskite material.The test result of other embodiment and embodiment 1, embodiment 2
It is similar, the perovskite material of corresponding chemical formula has been prepared.And the perovskite material being prepared does not have impurity phase, purity
It is high.
5 perovskite material sample 1 of embodiment#~10#Fluorescence property
Fluorometric investigation is carried out to the perovskite material obtained in embodiment 1 to embodiment 3, test result is similar with Fig. 3,
The portable ultraviolet detection light irradiations of ZF-7A are used under conditions of dark, and the sparkling crystal of green is presented.
Sample 1#~10#Show same fluorescence property.
6 perovskite material sample 1 of embodiment#~10#Fluorescence analysis
Fluorescence spectrum test is carried out to the perovskite material obtained in embodiment 1 to embodiment 3.Emission wavelength is in 490nm
It is adjustable between~520nm.Typical fluorogram is as shown in figure 4, counter sample 2#.Fig. 4 can be seen that hydridization perovskite crystallite
Luminescent material luminous efficiency is high, and it is good that fluorescence quantum yield can reach 80% or more, stability.
Sample 1#~10#Show similar fluorescence spectrum.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, makes a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of hydridization perovskite micro crystal material, which is characterized in that the hydridization perovskite micro crystal material includes chemical formula such as Formulas I
Shown in perovskite and the chemical formula perovskite as shown in Formula II;
AM2X5Formulas I;
A4MX6Formula II;
In perovskite insertion perovskite as shown in Formula II shown in formula I;
Wherein, A is selected from CH3NH3 +, NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;
R2Selected from hydrogen, C1~C10Alkyl, C1~C10Unsaturated alkyl;
M is metal ion, and the metal is selected from least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl, Ag;
X is selected from least one of halide anion.
2. hydridization perovskite micro crystal material according to claim 1, which is characterized in that the R2Selected from hydrogen, C1~C4Alkane
Base;
X is selected from Cl-、Br-、I-At least one of.
3. hydridization perovskite micro crystal material according to claim 1, which is characterized in that the hydridization perovskite micro crystal material
Scale be 0.001mm~200mm;
The size of the hydridization perovskite micro crystal material is 101~104mm3。
4. hydridization perovskite micro crystal material according to claim 1, which is characterized in that the hydridization perovskite micro crystal material
Emission wavelength be 300nm~1000nm.
5. hydridization perovskite micro crystal material according to claim 1, which is characterized in that the hydridization perovskite micro crystal material
Fluorescence quantum yield reach 80% or more.
6. the preparation method of hydridization perovskite micro crystal material described in any one of claim 1 to 5, which is characterized in that at least wrap
Include following steps:
S1) additive is added in the solution containing perovskite presoma, obtains solid-liquid two-phase mixtures system I;
S2) by step S1) described in solid-liquid two-phase mixtures system I reaction, obtain perovskite micro crystal material.
7. according to the method described in claim 6, it is characterized in that, step S1) described in additive be selected from R31-COOH、R32-
OH、R33-SH、R34It is at least a kind of in-C=S;
Wherein, R31、R32、R33、R34Independently selected from C1~C18Alkyl, C1~C18Unsaturated alkyl;
Preferably, step S1) described in additive it is at least a kind of in ethyl alcohol, oleic acid.
8. according to the method described in claim 6, it is characterized in that, step S1) described in perovskite presoma include organic ammonium
Salt AX1With metal salt MX2;
Wherein, the A is selected from CH3NH3 +, NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;
M is metal ion, and the metal is selected from least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl, Ag;
The X1、X2Independently selected from least one of halide anion;
Preferably, the organic ammonium salt AX1With metal salt MX2Molar ratio be 1:1~10;
Preferably, the organic ammonium salt AX1Ratio with additive is 1:(1~100) mol/ μ L;
Preferably, step S1) described in the solvent of solution be selected from least one of DMF, HBr, DMSO;
Preferably, the organic ammonium salt AX1And the ratio of solvent is 1:(2~10) mol/L;
It is further preferred that step S1) in solvent be DMF and HBr volume ratios be 1:The mixed solvent of (0.1~10).
9. according to the method described in claim 6, it is characterized in that, step S2) described in the condition reacted be selected from stirring, rub
At least one of wipe, is ultrasonic, shaking, heat;
Preferably, the reaction condition of the stirring is magnetic agitation, mechanical agitation or high speed dispersion, and the reaction time is 30~120
Minute, mixing speed is 80~100r/min;
The reaction condition of the friction is mechanical attrition method, and the reaction time is 30~120 minutes, drum speed 23.8r/min,
Steel ball size is 100mm;
The reaction condition of the ultrasound is that ultrasonic time is 30~120 minutes, and supersonic frequency is 40~60KHz, power 100W;
The reaction condition of the concussion shakes for water bath with thermostatic control, and the reaction time is 30~120 minutes, and concussion frequency is 80~100
Secondary/min, amplitude 40mm, bath temperature are 50~80 DEG C;
The reaction condition of the heating be 20~60 minutes in the reaction time, be heated to 80~100 DEG C;
Preferably, step S2) it includes at least:By S1) obtained mixed system I dissolves by heating, obtain solution II;Solution II is existed
80~100 DEG C are kept for 20~60 minutes, then continuously decrease temperature to seeded growth after 60~10 DEG C, 2~4 days, 25~35 days
After can be obtained the hydridization perovskite micro crystal material;
It is further preferred that step S2) in by S1) obtained mixed system I heating water baths dissolve to 80~100 DEG C;
It is further preferred that step S2) in obtained hydridization perovskite crystal washed through butyrolactone and toluene.
10. a kind of luminescent material, which is characterized in that comprising any one of claim 1 to 5 hydridization perovskite micro crystal material,
At least one of the hydridization perovskite micro crystal material being prepared according to claim 6 to 9 any one of them method.
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CN113604881A (en) * | 2021-07-05 | 2021-11-05 | 中山大学 | Narrow-band-gap alloy perovskite microcrystal and preparation method and application thereof |
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