CN107445842B - The preparation method of large scale mixed halogen methylamine lead bromine chlorine crystal - Google Patents
The preparation method of large scale mixed halogen methylamine lead bromine chlorine crystal Download PDFInfo
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- CN107445842B CN107445842B CN201710396945.3A CN201710396945A CN107445842B CN 107445842 B CN107445842 B CN 107445842B CN 201710396945 A CN201710396945 A CN 201710396945A CN 107445842 B CN107445842 B CN 107445842B
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- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 12
- 150000002367 halogens Chemical class 0.000 title claims abstract description 12
- DTAHKBOYTLIIKF-UHFFFAOYSA-N [Cl].[Br].[Pb].CN Chemical compound [Cl].[Br].[Pb].CN DTAHKBOYTLIIKF-UHFFFAOYSA-N 0.000 title abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012452 mother liquor Substances 0.000 claims abstract description 10
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000010792 warming Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 15
- 239000005457 ice water Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 abstract description 40
- 239000000463 material Substances 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation methods of large scale mixed halogen methylamine lead bromine chlorine crystal, include the following steps：Monomethylamine aqueous solution and the stirring of hydrobromic acid water are evaporated；Monomethylamine aqueous solution and hydrochloric acid stirring are evaporated by step S2；Step S3, by PbBr2With CH3NH3Br and PbCl2With CH3NH3Cl is dissolved in DMF and obtains CH with DMSO solvents3NH3Pb(Br1‑xClx)3Mother liquor；Change PbBr2/PbCl2Molar ratio obtains the different CH of x3NH3Pb(Br1‑xClx)3Mother liquor；Step S4, by CH3NH3Pb(Br1‑xClx)3Mother liquor is warming up to 95 105 DEG C, and constant temperature to crystal is precipitated, and is taken out when crystalline size is no longer grown up.The present invention can obtain the CH of different halogen ratios by changing material rate3NH3Pb(Br1‑xClx)3Crystal.
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 chlorine crystal
Preparation method is a kind of method for manually cultivating crystal using solution inversion growth method.
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 receive extensive attention.Base
In perovskite material solar battery efficiency more than 21%, show good development prospect.Relative to traditional list
Crystal silicon, polysilicon solar cell are expected to advantages such as cheap cost of material, simple technology of preparing, low temperature preparations
As the substitute of silica-based solar cell.CH3NH3PbX3Photoelectric properties and its halogens ingredient have prodigious relationship, lead to
It crosses and changes halogens ingredient and proportion and can reach continuous regulation and control to its optical band gap and wavelength of fluorescence.For example use Br
Element substitution CH3NH3PbCl3In Cl elements, the difference of Br constituent contents, gained compound CH3NH3Pb(Br1-xClx)3Band
Gap value also occurs to change accordingly, therefore CH3NH3Pb(Br1-xClx)3Crystal or film have weight in Novel Optoelectronic Device field
The application value wanted.At present to CH3NH3Pb(Br1-xClx)3Research based on thin-film material, there is no large scale CH3NH3Pb
(Br1-xClx)3The report of crystal growth.In order to obtain material structure and performance information, we are intended to prepare large scale CH3NH3Pb
(Br1-xClx)3Crystal, to study CH3NH3Pb(Br1-xClx)3Physical and chemical performance, optical property, electric property and the photo electric of material
Energy etc. provides material foundation, while by the research of these performances, is that optimization is based on CH3NH3Pb(Br1-xClx)3Photoelectric device
Performance material and theoretical foundation are provided.
Invention content
The purpose of the present invention is to provide a kind of large scale mixed halogen CH3NH3Pb(Br1-xClx)3The preparation side of crystal
Method, to study CH3NH3Pb(Br1-xClx)3Physical and chemical performance, optical property, electric property and photoelectric properties of material etc. provide material
Material basis.
A kind of large scale mixed halogen CH3NH3Pb(Br1-xClx)3The preparation method of crystal, 0 ＜ x ＜ 1, large scale refers to crystalline substance
The length and width of body reach 6-8mm, 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 item
It is mixed under part, is evaporated to obtain white powder object；
Step S2, CH3NH3It is prepared by Cl：By monomethylamine aqueous solution and aqueous hydrochloric acid solution by equimolar solute in ice-water bath item
It is mixed under part, is evaporated to obtain white powder object；
It is prepared by step S3, crystalline mother solution：By equimolar PbBr under normal temperature condition2With CH3NH3Br and equimolar PbCl2With
CH3NH3Cl is dissolved in N, the CH that N-dimethylformamide is saturated with dimethyl sulfoxide (DMSO) mixed solvent3NH3Pb(Br1-xClx)3It is female
Liquid；Change PbBr2/PbCl2Molar ratio obtains the CH of x difference values3NH3Pb(Br1-xClx)3Mother liquor；
Step S4, crystal growth are precipitated：By CH3NH3Pb(Br1-xClx)3Mother liquor is warming up to 95-105 DEG C, and constant temperature is until brilliant
Body is precipitated, and crystal is taken out when crystalline size is no longer grown up.
In a specific embodiment, the n,N dimethylformamide and dimethyl sulfoxide (DMSO) mixed solvent (DMF-DMSO)
By the N of isometric ratio, N-dimethylformamide and dimethyl sulfoxide (DMSO) 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, aqueous hydrochloric acid solution's mass percentage concentration is 37%.
Preferably, step S4 recrystallization temperatures are 100 DEG C.
Large scale CH prepared by the above method3NH3Pb(Br1-xClx)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 the ratio by changing raw material components can obtain different halogens
The adjustable CH of large scale, high quality, band gap of ratio3NH3Pb(Br1-xClx)3Crystal.
Description of the drawings
Fig. 1 is CH3NH3Pb(Br1-xClx)3Crystal preparation flow figure；
Fig. 2A is CH3NH3Pb(Br1-xClx)3Crystallogram (from left to right raw material PbBr2/PbCl2Molar ratio 3/1,2/
1,1/1,1/2,1/3), Fig. 2 B are the XRD spectrum of crystal shown in Fig. 2A；
Fig. 3 is CH3NH3Pb(Br1-xClx)3Crystal UV-VIS-NIR absorption spectrums (A) and its corresponding band gap spectrum (B).
Specific implementation mode
Technical scheme of the present invention is specifically introduced with reference to the accompanying drawings and examples.
Following embodiment agents useful for same are as follows：
PbBr2Solution, 99.99%, aladdin；
PbCl2Solution, 99.99%, aladdin；
HBr solution, 48wt%, AlfaAesar；
HCl solution, 37wt%, aladdin；
CH3NH2Solution, 40wt%, aladdin.
Embodiment 1CH3NH3Pb(Br1-xClx)3Preparation, x=0.5, that is, Br:Cl=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
Constant temperature is evaporated to obtain 1.12g white powder objects to your solute (0.01mol) at 100 DEG C after stirring 2h under the conditions of ice-water bath；
Step S2, CH3NH3It is prepared by Cl：By monomethylamine aqueous solution (40wt%) and aqueous hydrochloric acid solution (37wt%) by etc. rub
Constant temperature is evaporated to obtain 0.67g white powder objects to your solute (0.01mol) at 100 DEG C after stirring 2h under the conditions of ice-water bath；
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 PbCl2(0.01mol, 2.78g) and CH3NH3Cl (0.01mol, 0.67g) is dissolved in N, N dimethyl
Formamide and dimethyl sulfoxide (DMSO) mixed solvent (volume ratio 1:1,16ml) saturation CH is obtained3NH3Pb(Br1-xClx)3Mother liquor；
Step S4, crystal growth are precipitated：By CH3NH3Pb(Br1-xClx)3Mother liquor is warming up to 100 DEG C, and constant temperature is until crystal is analysed
Go out, crystal is taken out when crystalline size is no longer grown up, blot plane of crystal absorption liquid and dries.
Embodiment 2-4CH3NH3Pb(Br1-xClx)3Preparation
By adjusting PbBr2/PbCl2Molar ratio (PbBr2With CH3NH3Br equimolars, PbCl2With CH3NH3Cl equimolars) system
Standby Br:Cl molar ratios are respectively 3:1、2:1、1:2、1:3 crystal, other conditions are the same as embodiment 1.
5 physical parameter measurement of embodiment
CH prepared by embodiment 1-4 is measured respectively3NH3Pb(Br1-xClx)3Crystal (Br:Cl molar 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.
Measurement result is as shown in Figures 2 and 3, and the length and width of crystal reach 6-8mm, up to 2-4mm, have ideal spectrum
Matter, and band gap is adjustable, and quality is high.
The present invention uses inversion crystal growth from solution technique, and the ratio by changing raw material components can obtain different halogens
The adjustable CH of large scale, high quality, band gap of ratio3NH3Pb(Br1-xClx)3Crystal.Nearly hundred kinds of differences have also been attempted in applicant
Solvent, solvent combination and crystallization processes prepare large scale CH for crystallizing3NH3Pb(Br1-xClx)3Crystal, but it is undesirable,
Solubility is improper or gained crystal is irregular or crystallization is difficult to grow up, and is unable to get the large scale rule of the application
Then crystal.Large-size crystals of the present invention can be cut into the required material block of photoelectric field, be had to thin-film material
Power is supplemented.
The effect of above-described embodiment is only that the essentiality content for illustrating the present invention, but the guarantor of the present invention is not limited with this
Protect range.Essence and the guarantor that simply modification or simple replacement do not depart from technical solution of the present invention are carried out to technical solution of the present invention
Protect range.
Claims (6)
1. a kind of large scale mixed halogen CH3NH3Pb(Br1-xClx)3The preparation method of crystal, 0 ＜ x ＜ 1, large scale refers to crystal
It is long and wide up to 4-8mm, up to 2-4mm, which is characterized in that including following preparation process：
Step S1, CH3NH3It is prepared by Br：By monomethylamine aqueous solution and hydrobromic acid aqueous solution by equimolar solute under the conditions of ice-water bath
It is mixed, is evaporated to obtain white powder object；
Step S2, CH3NH3It is prepared by Cl：By monomethylamine aqueous solution and aqueous hydrochloric acid solution by equimolar solute under the conditions of ice-water bath
It is mixed, is evaporated to obtain white powder object；
It is prepared by step S3, crystalline mother solution：By equimolar PbBr under normal temperature condition2With CH3NH3Br and equimolar PbCl2With
CH3NH3Cl is dissolved in N, the CH that N-dimethylformamide is saturated with dimethyl sulfoxide (DMSO) mixed solvent3NH3Pb(Br1-xClx)3
Mother liquor；Change PbBr2/ PbCl2Molar ratio obtains the CH of x difference values3NH3Pb(Br1-xClx)3Mother liquor；
Step S4, crystal growth are precipitated：By CH3NH3Pb(Br1-xClx)3Mother liquor is warming up to 95-105 DEG C, and constant temperature is until crystal is analysed
Go out, 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 and dimethyl sulfoxide (DMSO)
By the N of isometric ratio, N-dimethylformamide and dimethyl sulfoxide (DMSO) are uniformly mixed mixed solvent.
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：Aqueous hydrochloric acid solution's mass percentage concentration is 37%.
6. preparation method according to claim 1, it is characterised in that：Step S4 recrystallization temperatures are 100 DEG C.
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| CN109468131B (en) * | 2018-11-01 | 2020-12-25 | 南京航空航天大学 | Organic-inorganic perovskite scintillator for nuclear radiation detection and preparation method thereof |
| CN110144625B (en) * | 2019-06-18 | 2021-01-05 | 山东科技大学 | Growing method of red-light octagonal lead-free two-dimensional perovskite single crystal |
| CN112210816B (en) * | 2020-09-29 | 2022-07-12 | 陕西师范大学 | Perovskite single crystal sheet, method for promoting growth of perovskite single crystal sheet and application of perovskite single crystal sheet |
Citations (2)
| 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 |
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Patent Citations (2)
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| CH3NH3PbBr3单晶的生长、结构与形貌;桑琳 等;《硅酸盐学报》;20160318;第44卷(第4期);第540-544页 * |
| 溶液法CH3NH3PbCl3单晶的生长与性能研究;王万富 等;《无机材料学报》;20160926;第31卷(第10期);第1063-1067页 * |
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