CN105350078B - A kind of method of quick preparation large area perovskite crystal - Google Patents

A kind of method of quick preparation large area perovskite crystal Download PDF

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CN105350078B
CN105350078B CN201510763073.0A CN201510763073A CN105350078B CN 105350078 B CN105350078 B CN 105350078B CN 201510763073 A CN201510763073 A CN 201510763073A CN 105350078 B CN105350078 B CN 105350078B
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perovskite
large area
perovskite crystal
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CN105350078A (en
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谢伟广
周洋洋
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Jinan University
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    • 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
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • 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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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention belongs to Semiconductor Optoeletronic Materials and device preparing technical field, disclose a kind of method of quick preparation large area perovskite crystal.This method includes the following steps：A certain amount of lead halide and methyl ammonium halide are weighed, is mixed, then adds in Isosorbide-5-Nitrae fourth lactones, dissolving obtains perovskite solution；Then gained perovskite solution is added in a certain amount of organic solvent, perovskite crystal is precipitated to obtain.Perovskite crystal is quickly precipitated by way of solution extracting in the present invention, this method is simple and practicable, it is reproducible, to extraneous of less demanding, but also different organic solvents can be selected to grow to obtain the single crystal grain of different sizes according to actual demand, its crystal grain sizes maximum is up to tens micro-meter scales so that it is making advantage of the photoelectric device etc. with bigger.

Description

A kind of method of quick preparation large area perovskite crystal
Technical field
The invention belongs to Semiconductor Optoeletronic Materials and device preparing technical field, more particularly to a kind of quickly to prepare big face The method of product perovskite crystal.
Background technology
Perovskite (CH3NH3PbI3, CH3NH3PbCl3, CH3NH3PbBr3) material is due to its high absorption coefficient, bipolarity Transmission electron hole, cheap and advantages such as convenient film deposition techniques and be widely used as solar cell active layer.At present Solar battery efficiency based on perovskite active layer has reached 20.1%.However, in perovskite active layer carrier diffusion Length, service life and mobility are to influence its key factor (Sum T C, Mathews N.Advancements in as battery perovskite solar cells:photophysics behind the photovoltaics[J].Energy& Environmental Science,2014,7(8):2518-2534.), crystallinity of these factors all with active layer film It is closely related with pattern.Experiment shows that perovskite single grain size is bigger, and carrier diffusion length is longer, defect state density Smaller (Shi D, Adinolfi V, Comin R, et al.Low trap-state density and long carrier diffusion in organoleadtrihalideperovskite single crystals[J].Science,2015, 347(6221):519-522.), these properties cause large size single crystal perovskite making photoelectric device etc. with bigger Advantage.
At present, perovskite crystal (CH is prepared3NH3PbI3) it is mainly the following method：(1) by controlling PbI2It is brilliant Body is added to CH3NH3(Yang S, Zheng Y C, Hou Y, et al.Formation Mechanism of are crystallized in I solution Freestanding CH3NH3PbI3Functional Crystals:In Situ Transformation vs Dissolution–Crystallization[J].Chemistry of Materials,2014,26(23):6705- 6710.)；(2) (Shi D, Adinolfi V, Comin R, et al.Low trap- are crystallized by reversed solution vapor auxiliary law statedensity and long carrier diffusion in organoleadtrihalideperovskite single crystals[J].Science,2015,347(6221):519-522.)；(3) it is crystallized by reverse dissolution degree method (Kadro J M,Nonomura K,Gachet D,et al.Facile route to freestanding CH3NH3PbI3crystals using inverse solubility[J].Scientific Reports,2015,5.).This Rate of crystalline growth prepared by a little methods is slower, and yield is relatively low, is unfavorable for preparing on a large scale.In order to overcome the above problem, need Further find the quick method for preparing large area perovskite crystal.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, the purpose of the present invention is to provide one kind quickly to prepare big face The method of product perovskite crystal.Perovskite crystal is quickly precipitated by way of solution extracting.
The purpose of the present invention is realized by following proposal：
A kind of method of quick preparation large area perovskite crystal, includes the following steps：
A certain amount of lead halide and methyl ammonium halide are weighed, is mixed, adds in 1,4-butyrolactone, dissolving obtains perovskite solution； Then gained perovskite solution is added in a certain amount of organic solvent, perovskite crystal is precipitated to obtain.
The lead halide can be lead chloride (PbCl2), lead bromide (PbBr2) and lead iodide (PbI2) in any one；
Preferably, the lead halide is lead iodide (PbI2)；
The methyl ammonium halide can be ammonio methacrylate (CH3NH3Cl), methyl bromide ammonium (CH3NH3) and methyl iodide Br Change ammonium (CH3NH3I any one in).
Preferably, the methyl ammonium halide is methylpyridinium iodide ammonium (CH3NH3I)。
Lead halide used and the molar ratio of methyl ammonium halide can be 1:1~3:1.
Preferably, the molar ratio of lead halide used and methyl ammonium halide is 1:1.
The concentration of the perovskite solution can be (0.5~1) mol/L.
Preferably, a concentration of 1mol/L of the perovskite solution.
The dissolving can be to dissolve by heating.
Preferably, the dissolving refers to dissolves by heating 1.5h at 60 DEG C.
The organic solvent can be dimethicone, dimethylformamide, dimethyl sulfoxide (DMSO), ether and toluene in extremely Few one kind.
Preferably, the organic solvent is at least one of dimethicone, dimethylformamide and ether.
The temperature of the organic solvent can be room temperature~150 DEG C, since different organic solvents are abundant with 1,4-butyrolactone Solution rate is different, organic solvent can be made to be mixed rapidly with 1,4-butyrolactone by heating.
Perovskite solution used and the volume ratio of organic solvent are (5~15):(1000~2000).
The present invention mechanism be：
1,4-butyrolactone is to dissolve the fine solvent of perovskite material, and in the 1,4-butyrolactone solution dissolved with perovskite There are many perovskite colloid (sizes<100nm).If the 1,4- butyrolactone solution for dissolving perovskite is added to organic solvent In, according to organic solvent similar compatibility principle, various organic solvents can extract 1,4-butyrolactone from perovskite solution, Remaining perovskite colloidal particle is recrystallized and is grown up.After 1,4-butyrolactone is extracted completely, under crystal size is just fixed Come, do not continue to recrystallize, because at this time without the solvent of dissolving perovskite colloidal particle.So crystal is finally precipitated Size depend on organic solvent extract 1,4-butyrolactone rate, different organic solvents extract 1,4-butyrolactone rate not Together, cause the size for growing crystal also different.
The present invention is had the following advantages and advantageous effect relative to the prior art：
(1) method proposed by the present invention for preparing perovskite crystal is simple and practicable, reproducible, yield is high, to extraneous ring Border such as humidity, temperature etc. are of less demanding.
(2) by fast-growth perovskite single-crystal techniques proposed by the present invention, the monocrystalline of different sizes can be obtained Particle can select different organic solvents to grow according to actual demand, which is expected to be weighed in fields such as photoelectric devices It applies.
Description of the drawings
Fig. 1 is the perovskite monocrystalline that perovskite solution is grown in dimethylformamide, dimethicone and ether respectively The X-ray diffractogram of material.
Fig. 2 is the perovskite monocrystalline that perovskite solution is grown in dimethylformamide, dimethicone and ether respectively The scanning electron microscope (SEM) and optics picture of material.Wherein, (a) (c) (e) in Fig. 2 is perovskite solution in dimethicone The scanning electron microscope (SEM) and optics picture of the perovskite monocrystal material of growth；(b) in Fig. 2 is perovskite solution in dimethyl Scanning electron microscope (SEM) photo of the perovskite monocrystal material grown in formamide；(f) in Fig. 2 is perovskite solution in ether Scanning electron microscope (SEM) photo of the perovskite monocrystal material of growth from solution.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this.
Agents useful for same is commercially available in embodiment.
Embodiment 1
(1) by the PbI of 2.5mmol2Powder and 2.5mmol CH3NH3I powder mixes the vial for being put into 5mL, adds in 2.5mL1,4- butyrolactone are placed on heating stirring in 60 DEG C of constant temperature ovens until powder is completely dissolved after shaking up；
(2) 1mL dimethicones is taken to be placed in 5mL beakers, while beaker is placed in 150 DEG C of thermal station and is heated；
(3) after powder is completely dissolved in first step vial, 10 μ L perovskite solution is taken to be added in dimethicone, 30s forms the crystal of black at once.
X-ray diffractogram spectrum analysis (such as Fig. 1), SEM and optical photograph are carried out (such as to gained black crystals in embodiment 1 (a), (c), (e) in Fig. 2) analysis, confirmed, the black crystals of growth are perovskite crystal material.
Embodiment 2
(1) by the PbI of 2.5mmol2Powder and 2.5mmol CH3NH3I powder mixes the glass bottle for being put into 5mL, adds in 2.5mL1,4- butyrolactone are placed on heating stirring in 60 DEG C of constant temperature ovens until powder is completely dissolved after shaking up；
(2) 2mL dimethyl formamide solutions is taken to instill in 5mL beakers, while beaker is placed in 70 DEG C of thermal station and is heated；
(3) after powder is completely dissolved in first step glass, the perovskite solution instillation dimethylformamide for taking 5 μ L is molten In liquid, 24s forms black crystals.
To gained black crystals carry out X-ray diffractogram spectrum analysis (such as Fig. 1) in embodiment 2 and SEM takes pictures (in such as Fig. 2 (b)) analysis, confirmed, the black crystals of growth are perovskite monocrystal material.
Embodiment 3
(1) by the PbI of 2.5mmol2The CH of powder and 2.5mmol3NH3I powder mixes the glass bottle for being put into 5mL, adds in 2.5mL1,4- butyrolactone are placed on heating stirring in 60 DEG C of constant temperature ovens until powder is completely dissolved after shaking up；
(2) 1.5mL diethyl ether solutions is taken to instill in 5mL beakers, beaker does not heat；
(3) after powder is completely dissolved in first step glass, the perovskite solution of 15 μ L is taken to instill in diethyl ether solution, 26s forms black crystals.
To gained black crystals carry out X-ray diffractogram spectrum analysis (such as Fig. 1) in embodiment 3 and SEM takes pictures (in such as Fig. 2 (f)) analysis, confirmed, the black crystals of growth are perovskite monocrystal material.
From embodiment 1, in the embodiment 2 and embodiment 3 as can be seen that preparation side of perovskite crystal provided by the invention Method, crystal growth time about 30s substantially reduce crystal growth time, and wherein crystal grain sizes maximum is up to tens Micro-meter scale so that it is making advantage of the photoelectric device etc. with bigger.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (7)

  1. A kind of 1. method of quick preparation large area perovskite crystal, it is characterised in that comprise the steps of：It weighs a certain amount of Lead halide and methyl ammonium halide, mixing, add in Isosorbide-5-Nitrae-fourth lactones, dissolving, obtain perovskite solution；Then it is gained perovskite is molten Liquid is added in a certain amount of organic solvent, and perovskite crystal is precipitated to obtain；
    Lead halide used and the molar ratio of methyl ammonium halide are 1:1~3:1；The perovskite solution it is a concentration of (0.5~ 1)mol/L；
    The dissolving refers to dissolves by heating 1.5h at 60 DEG C；
    Perovskite solution used and the volume ratio of organic solvent are (5~15):(1000~2000).
  2. 2. the method for quick preparation large area perovskite crystal according to claim 1, it is characterised in that：The halogenation Lead is PbCl2、PbBr2And PbI2In any one；The methyl ammonium halide is CH3NH3Cl、CH3NH3Br and CH3NH3In I Any one.
  3. 3. the method for quick preparation large area perovskite crystal according to claim 1, it is characterised in that：The halogenation Lead is PbI2；The methyl ammonium halide is CH3NH3I。
  4. 4. the method for quick preparation large area perovskite crystal according to claim 1, it is characterised in that：Described is organic Solvent is at least one of dimethicone, dimethylformamide, dimethyl sulfoxide (DMSO), ether and toluene.
  5. 5. the method for quick preparation large area perovskite crystal according to claim 1, it is characterised in that：Described is organic Solvent is at least one of dimethicone, dimethylformamide and ether.
  6. 6. the method for quick preparation large area perovskite crystal according to claim 1, it is characterised in that：Halogenation used The molar ratio of lead and methyl ammonium halide is 1:1；A concentration of 1mol/L of the perovskite solution.
  7. 7. the method for quick preparation large area perovskite crystal according to claim 1, it is characterised in that：The dissolving Refer to and dissolve by heating；The temperature of the organic solvent is room temperature~150 DEG C.
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US11404657B2 (en) 2016-07-28 2022-08-02 The University Of Hong Kong Method of fabricating perovskite periodic nanostructure including solid-liquid-solid phase transformation
CN109790611A (en) 2016-08-24 2019-05-21 香港大学 Dual phase steel and its manufacturing method
CN106637403B (en) * 2016-11-28 2019-04-12 华中科技大学 A kind of preparation method of perovskite monocrystalline
CN108560056B (en) * 2018-05-17 2020-02-14 武汉大学 Two-dimensional perovskite single crystal material and preparation method thereof
CN108987588A (en) * 2018-07-24 2018-12-11 南京信息工程大学 Multiple groups part perovskite absorbed layer precursor solution and preparation method thereof
CN110552061A (en) * 2019-09-16 2019-12-10 武汉大学 Preparation method for growing perovskite single crystal by liquid-phase diffusion separation crystallization at room temperature
CN112981538A (en) * 2021-02-04 2021-06-18 广西大学 Method for growing large-size perovskite single crystal
CN113845428A (en) * 2021-09-10 2021-12-28 中国科学院上海光学精密机械研究所 Preparation method of perovskite material powder

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CN103956394B (en) * 2014-05-13 2016-08-24 国家纳米科学中心 A kind of method improving perovskite solar cell light-absorption layer performance
CN104250723B (en) * 2014-09-09 2017-02-15 许昌学院 Chemical method for in-situ large-area controlled synthesis of perovskite type CH3NH3PBI3 membrane material based on lead simple-substance membrane
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CN104716263B (en) * 2015-03-18 2017-05-03 河南科技大学 Method for preparing mixed halide compound perovskite CH3NH3PbI3-xClx gradient optical film
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