CN104141166B

CN104141166B - The preparation method of large scale perovskite structure methylamine bromine leading crystal

Info

Publication number: CN104141166B
Application number: CN201410340812.0A
Authority: CN
Inventors: 苏静; 仲坤; 缪菊红; 雷勇; 史鹏飞; 朱万祺
Original assignee: Nanjing University of Information Science and Technology
Current assignee: Nanjing University of Information Science and Technology
Priority date: 2014-07-17
Filing date: 2014-07-17
Publication date: 2016-05-25
Anticipated expiration: 2034-07-17
Also published as: CN104141166A

Abstract

The invention discloses the preparation method of large scale perovskite structure methylamine bromine leading crystal, by PbBr₂With the dissolving of HBr solution, obtain Pb²⁺-HBr solution; By HBr solution and CH₃NH₂Solution in molar ratio 1:1 mixes, and at 0 DEG C, reacts 2h, obtains CH₃NH₃Br solution; Then by Pb obtained above²⁺-HBr solution and CH₃NH₃Br solution mixes, and is placed in preheating 48h at 70 DEG C, obtains CH₃NH₃PbBr₃Supersaturated solution, filters, and obtains the yellow liquid of clarification, and preheating 12h in the water-bath of 70 DEG C, is cooled to 50 DEG C, and evaporation at constant temperature obtains CH₃NH₃PbBr₃Crystal. It is synthetic that in technique of the present invention, HBr solution had both participated in raw material, is again the solvent of crystal growth, has synthesis technique simple, the advantage that side reaction is few; Grower is simple and easy, can grow high-quality, large-sized crystal.

Description

The preparation method of large scale perovskite structure methylamine bromine leading crystal

Technical field

The present invention relates to the preparation method of large scale perovskite structure methylamine bromine leading crystal, is a kind of solution evaporation that adoptsArtificial method of cultivating crystal, belongs to crystalline material preparing technical field.

Background technology

From 2009 to 2013, CH₃NH₃PbX₃The power of (X=Cl, Br, I) Ca-Ti ore type solar cell transforms effectRate, from 3.8% to exceeding 15%, worldwide, reaches unprecedented temperature to the research of Ca-Ti ore type solar cell, selectedThe 2013 year ten large technological breakthroughs that " Science " magazine is announced. This class material has the carrier mobility that inorganic constituent element is high concurrentlyThe easy flexible processing characteristics good with organic constituent element, can absorb the broad-spectrum light from visible ray to wavelength 800nm efficiently, also hasCan be at TiO₂，Al₂O₃React directly synthetic feature Deng on porous material by solution chemistry, be applicable to the advantages such as coating processes. FromThe angle of commercial value, the energy loss (0.4eV) of its photovoltaic process is suitable with crystal silicon solar energy battery, far below traditionalDSSCs and organic solar batteries (being about 0.7eV – 0.8eV). In addition, perovskite structural material is absorbing blueness and green lightSub-aspect is better than silicon. The top scientist in a lot of photovoltaic solars field foretells CH optimistically₃NH₃PbX₃(X=Cl, Br, I) etc.Perovskite structural material will become the first-selection of high-efficient full solid-state solar cell of new generation. But from practical angle, this class tooThe performance of sun energy battery is also urgently optimized. Due to CH₃NH₃PbX₃There is the tired of changeable structure and growing technology in (X=Cl, Br, I)Difficulty, the optics of structural chemistry to this crystal, crystal chemistry, many uniquenesses, the aspects such as electricity and magnetic performance also exist allSuspicious asking. For CH₃NH₃PbBr₃Monocrystalline, the full-size that retrieval obtains is at present 2mm. In order to obtain material structure accuratelyAnd performance information, we adopt solution growth method to prepare the CH of large-size₃NH₃PbBr₃Monocrystalline is research CH₃NH₃PbBr₃MaterialThe physical and chemical performance of material, optical property, electric property and photoelectric properties etc. provides material foundation, simultaneously grinding by these performancesStudy carefully, for optimizing CH₃NH₃PbBr₃The performance of solar cell provides theoretical foundation.

Summary of the invention

For current large scale perovskite structure methylamine bromine leading crystal (CH₃NH₃PbBr₃Crystal) the shortcoming of technology of preparing,In order to obtain large-sized CH₃NH₃PbBr₃Monocrystalline, the new CH of special proposition₃NH₃PbBr₃The breeding method of monocrystalline.

The preparation method of large scale perovskite structure methylamine bromine leading crystal, adopts solution evaporation, comprises the steps:

1) by the PbBr of 0.01 mole₂The HBr solution that is 48% by 25ml mass concentration dissolves, preparation Pb²⁺-HBr solution;

2) by HBr solution and CH₃NH₂Solution in molar ratio 1:1 mixes, and at 0～10 DEG C, reacts 2h, obtains CH₃NH₃BrSolution;

3) Pb step 1) being obtained²⁺-HBr solution and step 2) CH that obtains₃NH₃Br solution mixes, wherein Pb²⁺WithCH₃NH₃The mol ratio of Br is 1:(1～2), be preferably 1:1.5; Be placed in preheating 48～72h at 60～70 DEG C, obtainCH₃NH₃PbBr₃Supersaturated solution, filters, and obtains the yellow liquid of clarification as CH₃NH₃PbBr₃The mother liquor of crystal growth;

4) mother liquor step 3) being obtained is preheating 12h-24h under saturation temperature, is then cooled to 50 with the speed of 1 DEG C/hDEG C, obtain orange red CH₃NH₃PbBr₃Crystal, at 50 DEG C of evaporation at constant temperatures to liquid level of solution higher than plane of crystal 2-3mm;

5) under 50 DEG C of temperature constant states, take out orange red CH₃NH₃PbBr₃Crystal, removes the solution of plane of crystal, obtains chiThe very little large scale CH that reaches 5mm₃NH₃PbBr₃Crystal, is large scale perovskite structure methylamine bromine leading crystal.

Step 1) and step 2) in the mass percentage concentration of HBr solution be 48%.

In step 1), adopt the PbBr of 0.01 mole₂With 25ml, 48% HBr solution dissolves, preparation Pb²⁺-HBr is moltenLiquid, PbBr in this step₂Determine to obtain the size of saturated solution and crystal with the proportionate relationship of HBr;

Step 2) middle CH₃NH₂The mass percentage concentration of solution is 40%.

In step 4), rate of temperature fall is 1 DEG C/h.

Beneficial effect:

1) technique of the present invention, it is synthetic that HBr solution had both participated in raw material, is again the solvent of crystal growth, has synthesis technique letterSingle, the advantage that side reaction is few;

2) the present invention is with PbBr₂, HBr solution, CH₃NH₂Solution is raw material, and grower is simple and easy, can grow high-quality,Large-sized crystal, the crystalline size growing is up to 5mm.

Brief description of the drawings

Fig. 1 is CH of the present invention₃NH₃PbBr₃Crystal preparation technology flow chart;

Fig. 2 CH₃NH₃PbBr₃Crystal prototype picture;

Fig. 3 CH₃NH₃PbBr₃The XRD collection of illustrative plates of crystal.

Detailed description of the invention

Now in conjunction with the embodiments, the present invention is described in further detail as follows:

The purity of experiment agents useful for same is

PbBr₂(solute) purity 99.99%

HBr(solution) concentration expressed in percentage by weight 48%

CH₃NH₂(solution) concentration expressed in percentage by weight 40%

Embodiment 1:

The preparation method of large scale perovskite structure methylamine bromine leading crystal, step is as follows:

1) take the PbBr of 0.01mol₂, with 25ml, the HBr solution that mass concentration is 48% at room temperature dissolves, preparation Pb² ⁺-HBr solution;

2) according to HBr and CH₃NH₂Mol ratio be 1:1, measure respectively the HBr solution of mass concentration 48%, mass concentration40% CH₃NH₂The each 2.32ml of solution, 1.72ml, mixes these two solution and sealing, is placed in 0 DEG C of ice-water bath 2h, obtainsCH₃NH₃Br solution;

3) at room temperature, by Pb²⁺-HBr solution and CH₃NH₃Br solution mixes, and orange red solids appears in bottom at onceMatter, is placed in 70 DEG C of water-bath preheating 48h by this solution;

4) keeping solution temperature is in 70 DEG C of situations, removes by filter orange red solid matter. By the yellow of the clarification obtainingLiquid is as CH₃NH₃PbBr₃The mother liquor of crystal growth;

5) above-mentioned mother liquor is positioned over to preheating 12h in the water-bath of 70 DEG C;

6) design cooling process, rate of temperature fall is 1 DEG C/h, and solution temperature is dropped to 50 DEG C, at 50 DEG C of evaporation at constant temperatures, steamsSend to liquid level of solution higher than plane of crystal 2mm;

7) under 50 DEG C of constant temperatures, separate out liquid, orange red bottom crystal is carefully taken out;

8) blot the solution of plane of crystal with filter paper, obtain being of a size of the CH of 5mm₃NH₃PbBr₃Crystal.

Fig. 1 is CH₃NH₃PbBr₃Crystal preparation flow figure, Fig. 2 is for obtaining CH₃NH₃PbBr₃Crystallogram, crystalline sizeGreatly, crystal face is bright and clean. Fig. 3 is CH₃NH₃PbBr₃The XRD collection of illustrative plates of crystal, confirms that obtaining crystal is cubic system CH₃NH₃PbBr₃BrilliantBody.

These results suggest that, adopt above solwution method evaporation crystal growth technique, can obtain large-size, high-qualityCH₃NH₃PbBr₃Crystal.

Claims

1. the preparation method of large scale perovskite structure methylamine bromine leading crystal, is characterized in that being: adopt solution evaporation, compriseFollowing steps:

2) by HBr solution and CH₃NH₂Solution in molar ratio 1:1 mixes, and at 0～10 DEG C, reacts 2h, obtains CH₃NH₃Br solution;

3) Pb step 1) being obtained²⁺-HBr solution and step 2) CH that obtains₃NH₃Br solution mixes, wherein Pb²⁺WithCH₃NH₃The mol ratio of Br is 1:1～2; Be placed in preheating 48～72h at 60～70 DEG C, obtain CH₃NH₃PbBr₃Supersaturated solution,Filter, obtain the yellow liquid of clarification as CH₃NH₃PbBr₃The mother liquor of crystal growth;

4) mother liquor step 3) being obtained is preheating 12h-24h at 60～70 DEG C, is then cooled to 50 DEG C, obtains orange redCH₃NH₃PbBr₃Crystal, at 50 DEG C of evaporation at constant temperatures to liquid level of solution higher than plane of crystal 2-3mm;

5) under 50 DEG C of temperature constant states, take out orange red CH₃NH₃PbBr₃Crystal, removes the solution of plane of crystal, obtains size and reachesThe large scale CH of 5mm₃NH₃PbBr₃Crystal, i.e. large scale perovskite structure methylamine bromine leading crystal.

2. the preparation method of large scale perovskite structure methylamine bromine leading crystal according to claim 1, is characterized in that being:Step 2) in the mass percentage concentration of HBr solution be 48%.

3. the preparation method of large scale perovskite structure methylamine bromine leading crystal according to claim 1, is characterized in that being:Step 2) middle CH₃NH₂The mass percentage concentration of solution is 40%.

4. the preparation method of large scale perovskite structure methylamine bromine leading crystal according to claim 1, is characterized in that being:In step 4), cooling declines with the speed of 1 DEG C/h.

5. the preparation method of large scale perovskite structure methylamine bromine leading crystal according to claim 1, is characterized in that being:Pb in step 3)²⁺With CH₃NH₃The mol ratio of Br is 1:1.5.