CN107141222A - The preparation method of large scale mixed halogen methylamine lead bromine iodine crystal - Google Patents
The preparation method of large scale mixed halogen methylamine lead bromine iodine crystal Download PDFInfo
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- CN107141222A CN107141222A CN201710396953.8A CN201710396953A CN107141222A CN 107141222 A CN107141222 A CN 107141222A CN 201710396953 A CN201710396953 A CN 201710396953A CN 107141222 A CN107141222 A CN 107141222A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses the preparation method of large scale mixed halogen methylamine lead bromine iodine crystal, 0 ＜ x ＜ 1, crystalline form is quadrangle or hexagon cube, and large scale refers to the length of side 2 10mm, high 2 4mm, including：Step S1, by monomethylamine aqueous solution and hydrobromic acid aqueous solution by etc. the solute that rubs mix and be evaporated in ice-water bath condition；Step S2, by monomethylamine aqueous solution and hydriodic acid aqueous solution by etc. the solute that rubs mix and be evaporated in ice-water bath condition；Step S3, normal temperature by etc. the PbBr that rubs2With CH3NH3Br and wait the PbI that rubs2With CH3NH3I is dissolved in N, and N-dimethylformamide obtains mother liquor with gamma butyrolactone mixed solvent；Change PbBr2/PbI2Mol ratio obtains the different mother liquors of x；Step S4,95 105 DEG C are warming up to by mother liquor, are separated out, are taken out when crystalline size is no longer grown up to crystal.
Description
Technical field
The invention belongs to crystalline material preparing technical field, it is related to a kind of large scale mixed halogen methylamine lead bromine iodine crystal
Preparation method, is a kind of method that use solution inversion growth method manually cultivates crystal.
Background technology
Nearest hybrid inorganic-organic perovskite material (CH3NH3PbX3, X=I, Br, Cl) and because it is in solar cell, hair
The fields such as optical diode, photodetector show excellent optical property and electrical properties and widely paid close attention to.Base
In perovskite material solar battery efficiency more than 21%, show good development prospect.Relative to traditional list
Crystal silicon, polysilicon solar cell, it has the advantages such as cheap cost of material, simple technology of preparing, low temperature preparation, is expected to
Substitute as silica-based solar cell.CH3NH3PbX3Photoelectric properties and its halogens composition have very big relation, lead to
The continuous regulation and control to its optical band gap and wavelength of fluorescence can be reached by crossing change halogens composition and proportion.Such as use Br
Element substitution CH3NH3PbI3In I elements, the difference of Br constituent contents, the compound CH of gained3NH3Pb(Br1-xIx)3Band
Corresponding change, therefore CH also occur for gap value3NH3Pb(Br1-xIx)3Crystal or film have important in Novel Optoelectronic Device field
Application value.At present to CH3NH3Pb(Br1-xIx)3Research based on thin-film material, there is no large scale CH3NH3Pb(Br1- xIx)3The report of crystal growth.In order to obtain material structure and performance information, we are intended to prepare large scale CH3NH3Pb(Br1- xIx)3Crystal, for research CH3NH3Pb(Br1-xIx)3Physical and chemical performance, optical property, electric property and photoelectric properties of material etc. are carried
For material foundation, while by the research of these performances, CH is based on for optimization3NH3Pb(Br1-xIx)3Photoelectric device performance
Material and theoretical foundation are provided.
The content of the invention
It is an object of the invention to provide a kind of large scale mixed halogen CH3NH3Pb(Br1-xIx)3The preparation method of crystal,
For research CH3NH3Pb(Br1-xIx)3Physical and chemical performance, optical property, electric property and photoelectric properties of material etc. provide material base
Plinth.
A kind of large scale mixed halogen CH3NH3Pb(Br1-xIx)3The preparation method of crystal, 0 ＜ x ＜ 1, crystal shape is four
Side shape or hexagon cube, large scale refer to the length of side up to 2-10mm, up to 2-4mm, including following preparation process：
Step S1, CH3NH3It is prepared by Br：By monomethylamine aqueous solution and hydrobromic acid aqueous solution by equimolar solute in ice-water bath bar
Mixed under part, be evaporated to obtain white powder thing；
Step S2, CH3NH3It is prepared by I：By monomethylamine aqueous solution and hydriodic acid aqueous solution by equimolar solute in ice-water bath bar
Mixed under part, be evaporated to obtain white powder thing；
It is prepared by step S3, crystalline mother solution：By equimolar PbBr under the conditions of 55-65 DEG C2With CH3NH3Br and equimolar PbI2
With CH3NH3I is dissolved in N, and N-dimethylformamide obtains the CH of saturation with gamma-butyrolacton mixed solvent3NH3Pb(Br1-xIx)3It is female
Liquid；Change PbBr2/PbI2Mol ratio obtains the CH of the different values of x3NH3Pb(Br1-xIx)3Mother liquor；
Step S4, crystal growth is separated out：By CH3NH3Pb(Br1-xIx)3Mother liquor is warming up to 95-105 DEG C, constant temperature until crystal
Separate out, crystal is taken out when crystalline size is no longer grown up.
In a specific embodiment, the DMF and gamma-butyrolacton mixed solvent (DMF-DMSO) by
The N of isometric ratio, N-dimethylformamide and gamma-butyrolacton are uniformly mixed.
In a specific embodiment, monomethylamine aqueous solution mass percentage concentration is 40%.
In a specific embodiment, hydrobromic acid aqueous solution mass percentage concentration is 48%.
In a specific embodiment, hydriodic acid aqueous solution mass percentage concentration is 57%.
Preferably, step S4 recrystallization temperatures are 100 DEG C, and step S3 solution temperatures are 60 DEG C.
Large scale CH prepared by the above method3NH3Pb(Br1-xIx)3Application of the crystal in field of photoelectric devices.
Beneficial effects of the present invention：
The present invention uses inversion crystal growth from solution technique, and different halogens can be obtained by the ratio for changing raw material components
The large scale of ratio, the adjustable CH of high-quality, band gap3NH3Pb(Br1-xIx)3Crystal.
Brief description of the drawings
Fig. 1 is CH3NH3Pb(Br1-xIx)3Crystal preparation flow figure；
Fig. 2A is CH3NH3Pb(Br1-xIx)3Crystallogram (from left to right raw material PbBr2/PbI2Mol ratio 3/1,2/1,
1/1st, 1/2,1/3), Fig. 2 B are the XRD spectrum of crystal shown in Fig. 2A；
Fig. 3 is CH3NH3Pb(Br1-xIx)3Crystal UV-VIS-NIR absorption spectrums (A) and its corresponding band gap spectrum (B).
Embodiment
Technical scheme is specifically introduced with reference to the accompanying drawings and examples.
Following embodiment agents useful for same are as follows：
PbBr2Solution, 99.99%, aladdin；
PbI2Solution, 99.99%, aladdin；
HBr solution, 48wt%, AlfaAesar；
HI solution, 57wt%, aladdin；
CH3NH2Solution, 40wt%, aladdin.
Embodiment 1CH3NH3Pb(Br1-xIx)3Preparation, x=0.5 is Br:I=1:1
Including following preparation process (flow is as shown in Figure 1)：
Step S1, CH3NH3It is prepared by Br：By monomethylamine aqueous solution (40wt%) and hydrobromic acid aqueous solution (48wt%) by etc. rub
Your solute (0.01mol) stirs 2h under the conditions of ice-water bath and is evaporated to obtain 1.12g white powder things after constant temperature at 100 DEG C；
Step S2, CH3NH3It is prepared by I：By monomethylamine aqueous solution (40wt%) and hydriodic acid aqueous solution (57wt%) by etc. rub
Your solute (0.01mol) stirs 2h under the conditions of ice-water bath and is evaporated to obtain 1.59g white powder things after constant temperature at 100 DEG C；
It is prepared by step S3, crystalline mother solution：By PbBr under normal temperature condition2(0.01mol, 3.67g) and CH3NH3Br
(0.01mol, 1.12g) and PbI2(0.01mol, 4.61g) and CH3NH3I (0.01mol, 1.59g) is dissolved in N, N dimethyl first
Acid amides and gamma-butyrolacton mixed solvent (volume ratio 1:1,16ml) saturation CH is obtained3NH3Pb(Br1-xIx)3Mother liquor；
Step S4, crystal growth is separated out：By CH3NH3Pb(Br1-xIx)3Mother liquor is warming up to 100 DEG C, constant temperature until crystal is analysed
Go out, crystal is taken out when crystalline size is no longer grown up, blot plane of crystal adsorptive liquid and dry.
Embodiment 2-4CH3NH3Pb(Br1-xIx)3Preparation
By adjusting PbBr2/PbI2Mol ratio (PbBr2With CH3NH3Br equimolars, PbI2With CH3NH3I equimolars) prepare
Br:I mol ratios are respectively 3:1、2:1、1:2、1:3 crystal, other conditions be the same as Example 1.
The physical parameter measurement of embodiment 5
CH prepared by embodiment 1-4 is determined respectively3NH3Pb(Br1-xIx)3Crystal (Br:I mol ratios are respectively 3:1、2:1、
1:1、1:2、1:3) size, XRD, UV-VIS-NIR absorption spectrum and its corresponding band gap spectrum.
As shown in Figures 2 and 3, crystal shape is quadrangle or hexagon cube to measurement result, and large scale refers to the length of side and reached
2-10mm, up to 2-4mm, with preferable spectral quality, and band gap is adjustable, and quality is high.
The present invention uses inversion crystal growth from solution technique, and different halogens can be obtained by the ratio for changing raw material components
The large scale of ratio, the adjustable CH of high-quality, band gap3NH3Pb(Br1-xIx)3Crystal.It is molten that applicant have also been attempted nearly hundred kinds of differences
Agent, solvent combination and crystallization processes, which are used to crystallize, prepares large scale CH3NH3Pb(Br1-xIx)3Crystal, but it is undesirable, or
Solubility is improper, otherwise gained crystal is irregular, otherwise crystallization is difficult to grow up, it is impossible to and the large scale rule for obtaining the application is brilliant
Body.Large-size crystals of the present invention can be cut into the material block required for photoelectric field, be the strong benefit to thin-film material
Fill.
The effect of above-described embodiment is only that the essentiality content of the explanation present invention, but the guarantor of the present invention is not limited with this
Protect scope.Simply modification is carried out to technical solution of the present invention or simple replacement does not depart from essence and the guarantor of technical solution of the present invention
Protect scope.
Claims (8)
1. a kind of large scale mixed halogen CH3NH3Pb(Br1-xIx)3The preparation method of crystal, 0 ＜ x ＜ 1, crystal shape is four sides
Shape or hexagon cube, large scale refer to the length of side up to 2-10mm, up to 2-4mm, it is characterised in that comprise the following steps：
Step S1, CH3NH3It is prepared by Br：Monomethylamine aqueous solution and hydrobromic acid aqueous solution are pressed into equimolar solute under the conditions of ice-water bath
Mix, be evaporated to obtain white powder thing；
Step S2, CH3NH3It is prepared by I：Monomethylamine aqueous solution and hydriodic acid aqueous solution are pressed into equimolar solute under the conditions of ice-water bath
Mix, be evaporated to obtain white powder thing；
It is prepared by step S3, crystalline mother solution：By equimolar PbBr under the conditions of 55-65 DEG C2With CH3NH3Br and equimolar PbI2With
CH3NH3I is dissolved in N, and N-dimethylformamide obtains the CH of saturation with gamma-butyrolacton mixed solvent3NH3Pb(Br1-xIx)3Mother liquor；
Change PbBr2/PbI2Mol ratio obtains the CH of the different values of x3NH3Pb(Br1-xIx)3Mother liquor；
Step S4, crystal growth is separated out：By CH3NH3Pb(Br1-xIx)3Mother liquor is warming up to 95-105 DEG C, and constant temperature is separated out up to crystal,
Crystal is taken out when crystalline size is no longer grown up.
2. preparation method according to claim 1, it is characterised in that：The N, N-dimethylformamide is mixed with gamma-butyrolacton
Bonding solvent is by the N of isometric ratio, and N-dimethylformamide and gamma-butyrolacton are uniformly mixed.
3. preparation method according to claim 1, it is characterised in that：Monomethylamine aqueous solution mass percentage concentration is 40%.
4. preparation method according to claim 1, it is characterised in that：Hydrobromic acid aqueous solution mass percentage concentration is 48%.
5. preparation method according to claim 1, it is characterised in that：Hydriodic acid aqueous solution mass percentage concentration is 57%.
6. preparation method according to claim 1, it is characterised in that：Step S4 recrystallization temperatures are 100 DEG C.
7. preparation method according to claim 1, it is characterised in that：Step S3 solution temperatures are 60 DEG C.
8. large scale CH prepared by claim 1-73NH3Pb(Br1-xIx)3Application of the crystal in field of photoelectric devices.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108842185A (en) * | 2018-06-06 | 2018-11-20 | 太原理工大学 | A kind of methylamine lead iodine perovskite monocrystalline thin slice for photodetection |
| EP3991220A4 (en) * | 2019-06-28 | 2023-07-19 | The Regents of the University of California | Strain engineering and epitaxial stabilization of halide perovskites |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104131352A (en) * | 2014-07-17 | 2014-11-05 | 南京信息工程大学 | Preparation method of large-sized perovskite structure CH3NH3PbI3 crystal |
| CN104141166A (en) * | 2014-07-17 | 2014-11-12 | 南京信息工程大学 | Preparing method for methylamine bromide lead crystals of large-size perovskite structure |
| CN105820055A (en) * | 2016-01-25 | 2016-08-03 | 湖北大学 | Methyl amino lead iodide bismuth perovskite crystal light absorption layer material and preparation method thereof |
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2017
- 2017-05-31 CN CN201710396953.8A patent/CN107141222B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104131352A (en) * | 2014-07-17 | 2014-11-05 | 南京信息工程大学 | Preparation method of large-sized perovskite structure CH3NH3PbI3 crystal |
| CN104141166A (en) * | 2014-07-17 | 2014-11-12 | 南京信息工程大学 | Preparing method for methylamine bromide lead crystals of large-size perovskite structure |
| CN105820055A (en) * | 2016-01-25 | 2016-08-03 | 湖北大学 | Methyl amino lead iodide bismuth perovskite crystal light absorption layer material and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| 桑琳 等: "CH3NH3PbBr3单晶的生长、结构与形貌", 《硅酸盐学报》 * |
| 王万富 等: "溶液法CH3NH3PbCl3单晶的生长与性能研究", 《无机材料学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108842185A (en) * | 2018-06-06 | 2018-11-20 | 太原理工大学 | A kind of methylamine lead iodine perovskite monocrystalline thin slice for photodetection |
| EP3991220A4 (en) * | 2019-06-28 | 2023-07-19 | The Regents of the University of California | Strain engineering and epitaxial stabilization of halide perovskites |
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| CN107141222B (en) | 2018-07-24 |
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