CN110541187B - Perovskite single crystal with light trapping structure and preparation method thereof - Google Patents

Perovskite single crystal with light trapping structure and preparation method thereof Download PDF

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CN110541187B
CN110541187B CN201910959359.4A CN201910959359A CN110541187B CN 110541187 B CN110541187 B CN 110541187B CN 201910959359 A CN201910959359 A CN 201910959359A CN 110541187 B CN110541187 B CN 110541187B
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single crystal
template
light trapping
perovskite
trapping structure
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CN110541187A (en
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刘生忠
张云霞
刘渝城
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Shaanxi Normal 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
    • C30B29/12—Halides
    • 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
    • C30B7/005—Epitaxial layer growth

Abstract

The perovskite single crystal with the light trapping structure and the preparation method thereof have the advantages of simple operation, high success rate, in-situ growth capability and light trapping structure qualityHigh. The preparation method comprises the steps of putting a template with a light trapping structure on the surface into ABX after activation treatment3In the perovskite precursor solution, the precursor solution performs heterogeneous nucleation on the surface of a template with a light trapping structure, and then ABX with the surface light trapping structure opposite to the surface light trapping structure of the template is grown in situ3A perovskite single crystal; wherein A is CH3NH3 +、H2N‑CH＝NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+(ii) a B is Pb, Ge or Sn; x is Cl, Br or I. By adopting a material with a stable light trapping structure as a template, the perovskite growth liquid performs heterogeneous nucleation on the template with the concave-convex surface structure, and then the perovskite single crystal with the surface light trapping structure opposite to the template structure is grown in situ.

Description

Perovskite single crystal with light trapping structure and preparation method thereof
Technical Field
The invention relates to the field of perovskite crystals, in particular to a perovskite single crystal with a light trapping structure and a preparation method thereof.
Background
In recent years, perovskite solar cells have received great attention in the field of photovoltaic solar cells due to their advantages of low cost, fast-increasing photoelectric conversion efficiency, and the like. At present, how to further improve the photoelectric conversion efficiency and stability of the perovskite cell is the most important research topic. Meanwhile, perovskite materials are also widely applied to the research of the optical detector. However, most perovskite solar cells are based on polycrystalline thin films. It is known that a single crystal material has a wider absorption range, a lower defect state density, a higher carrier mobility, a longer carrier lifetime, and better stability than a polycrystalline thin film because of no reaction interface such as a grain boundary, a grain gap, and the like. Therefore, solar cells based on single crystal perovskite materials will bring a new technological leap.
However, since the high-quality perovskite single crystal has a smooth surface structure, the reflection of light is greatly increased, so that the absorption of incident light is reduced, and the conversion efficiency of the solar cell and the response rate of a photodetector are further reduced. Therefore, it is necessary to find a method for changing the surface structure of the perovskite single crystal so as to reduce the reflection of light and further enhance the light absorption. However, since the perovskite single crystal is grown by a solution method, the solution is easy to change the surface appearance of the crystal for the second time, and therefore, the light trapping structure adopts a secondary chemical treatment method and cannot be formed at one time when the perovskite crystal is grown. At present, the preparation of perovskite single crystal with perfect surface light trapping structure is not disclosed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the perovskite single crystal with the light trapping structure and the preparation method thereof, the operation is simple, the success rate is high, the in-situ growth can be realized, and the light trapping structure is high in quality.
The invention is realized by the following technical scheme:
a process for preparing the perovskite monocrystal with light trapping structure includes activating the template with light trapping structure on its surface, and putting it in ABX3In the perovskite precursor solution, the precursor solution performs heterogeneous nucleation on the surface of a template with a light trapping structure, and then ABX with the surface light trapping structure opposite to the surface light trapping structure of the template is grown in situ3A perovskite single crystal; wherein A is CH3NH3 +、H2N-CH＝NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+(ii) a B is Pb, Ge or Sn; x is Cl, Br or I.
Preferably, the light trapping structure on the surface of the template is a rugged structure, and the rugged structure is a plurality of repeated unit structures.
Furthermore, the unit structure is a pyramid, inverted pyramid, spherical or hemispherical concave hole structure, and the diameter of the unit structure is 20nm-150 um.
Preferably, the template is a crystalline silicon with light trapping structure, a stainless steel or an array-arranged polystyrene bead plate.
Preferably, when the template is activated, the template is placed in a silane coupling agent with amino or mercapto groups and activated at a temperature of 50-70 ℃ for 10-60 minutes, so that a chemical group capable of simultaneously connecting the template and the perovskite is obtained on the surface of the template.
Preferably, according to ABX3Weighing halide containing A and a metal compound capable of providing a B source according to the stoichiometric ratio of the perovskite single crystal, and dissolving the halide and the metal compound in a solvent to obtain ABX with the concentration of 0.5-2.5 mol/L3A perovskite precursor solution.
Further, the metal compound providing a lead source is lead chloride (PbCl)2) Lead bromide (PbBr)2) Lead iodide (PbI)2) Or lead acetate (Pb (CH)3COO)2·xH2O)；
The metal compound for providing the tin source is stannous chloride (SnCl)2) Tin tetrachloride (SnCl)4) Stannous bromide (SnBr)2) Or tin iodide (SnI)2)；
The metal compound for providing the germanium source is germanium chloride (GeCl)2) Germanium bromide (GeBr)2) Or germanium iodide (GeI)2)；
The solvent is at least one of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
Preferably, ABX3When the perovskite precursor solution is subjected to single crystal growth on the template, the perovskite precursor solution is sealed, and the growth temperature is 40-120 ℃.
Preferably, the surface is grown in situ with ABX3Template of perovskite single crystal from ABX3Taking out the perovskite precursor solution, maintaining the growth temperature of the single crystal until no residual ABX is left on the surface3Cooling the perovskite precursor solution, separating the single crystal from the surface of the template, ABX3The separation surface of the perovskite single crystal forms a surface light trapping structure opposite to the surface light trapping structure of the template.
A perovskite single crystal with a light trapping structure prepared by any scheme above.
Compared with the prior art, the invention has the following beneficial technical effects:
the method adopts the template to carry out in-situ growth to obtain the ABX with the surface light trapping structure3The perovskite single crystal method has simple process, mild growth conditions, low equipment requirement and operabilityThe performance is strong. By adopting a material with a stable light trapping structure as a template, the perovskite growth liquid performs heterogeneous nucleation on the template with the concave-convex surface structure, and then the perovskite single crystal with the surface light trapping structure opposite to the template structure is grown in situ. Provides a new method for researching the intrinsic performance of the perovskite crystal material, and further provides a new research idea for improving the performance of the perovskite single crystal-based photoelectric device.
Drawings
FIG. 1 is a schematic flow chart of the operation of the method in an example of the present invention.
FIG. 2 is a surface topography of a perovskite single crystal prepared by the method described in the examples of the invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The method takes the material with the light trapping structure as the template, grows the perovskite single crystal material in situ in the solution, and has the advantages of simple process, strong operability and simple equipment requirement. The surface of the prepared perovskite single crystal has a light trapping structure, so that the light utilization rate of the perovskite single crystal is greatly improved. The solar cell assembled by the perovskite single crystal with the light trapping structure prepared by the invention can be expected to obtain higher photoelectric conversion efficiency. And the light detector manufactured by the perovskite single crystal with the light trapping structure prepared by the invention has higher light responsivity. The device also has better stability. Thereby promoting the application research of perovskite materials and related photoelectric devices (including solar cells, photodetectors and the like).
The invention adds a material with an optimized light trapping structure on the surface into a reaction system as a hard template, and then adds fresh ABX into the system3And (3) perovskite precursor solution, so that perovskite single crystal with a surface light trapping structure opposite to the template structure is grown in situ on the surface of the template. Specifically, a template with a light trapping structure on the surface is placed into ABX after being activated3In the perovskite precursor solution, the precursor solution performs heterogeneous nucleation on the surface of a template with a light trapping structure, and then a light trapping junction with the surface of the template grows in situABX with surface light trapping structure in reverse structure3A perovskite single crystal; wherein A is CH3NH3 +、H2N-CH＝NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+(ii) a B is Pb, Ge or Sn; x is Cl, Br or I.
The material with the surface light trapping structure is provided with a rugged structure on the surface so as to form the light trapping structure. The rugged structure is a plurality of repeated unit structures, and the plurality of unit structures are arranged in an array in the preferred embodiment. The unit structure can be a pyramid, an inverted pyramid, a spherical or a hemispherical concave hole structure. The diameter of the unit structure is 20nm-150 um.
The template exists stably in the perovskite precursor solution, and the structure is not damaged. The modified surface can form chemical bonds with the perovskite so as to improve the adhesion of the interface. The material for modifying the surface of the template may be a silane coupling agent having an amino or mercapto group, such as 3-Aminopropyltriethoxysilane (APTES), mercaptopropyltrimethoxysilane or 3-aminopropyltrimethoxysilane. The template can be crystalline silicon with light trapping structures, stainless steel or Polystyrene (PS) bead plates arranged in an array, and the like.
When the template is activated, the template is placed in a silane coupling agent with amino or sulfhydryl groups and is activated for 10-60 minutes at the temperature of 50-70 ℃, so that chemical groups capable of simultaneously connecting the template and perovskite are obtained on the surface of the template. In the preferred embodiment, the silane coupling agent with amino or mercapto group is diluted by chlorobenzene and then the template is activated, and the reaction between silicon and the silane coupling agent is controlled by slowing down the reaction rate after dilution, and the silane coupling agent can be o-dichlorobenzene as the diluent, so long as the silane coupling agent can be well dispersed without damaging the solvent of the template structure.
ABX with surface light trapping structure obtained by the method3Perovskite single crystal, wherein A is CH3NH3 +、H2N-CH＝NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+(ii) a B is Pb2+、Ge2+Or Sn2+(ii) a X is Cl-、Br-Or I-. During preparation, the precursor solution containing organic/inorganic halide, metal compound capable of providing lead source, tin source or germanium source and the statistic capable of dissolving these two compounds is prepared into crystal growth. And then putting the clean light trapping structure template and the precursor solution into a reaction container, and further gradually heating to grow the perovskite single crystal with the surface light trapping structure, as shown in figure 1.
ABX with surface light trapping structure3The perovskite single crystal growth method comprises the following specific steps as shown in figure 1:
step 1, cleaning a template material with a light trapping structure to obtain a material with a clean surface.
Step 2, carrying out surface modification treatment on the template with the light trapping structure: the template was placed in a mixture of chlorobenzene 10: 1, activating the 3-aminopropyl triethoxysilane after dilution for 10-60 minutes at 50-70 ℃, thereby obtaining a chemical group capable of forming a chemical bond with the perovskite on the surface of the template.
Step 3, preparing a precursor single crystal growth solution: weighing stoichiometric ratio of organic/inorganic halide and compound capable of providing metal source, dissolving in solvent to obtain clear and transparent ABX3Perovskite single crystal precursor single crystal growth liquid.
The perovskite single crystal precursor solution may be ABX3Form (A) is CH3NH3 +、H2N-CH＝NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+(ii) a B is Pb, Ge or Sn; x is Cl, Br or I. Taking metal compounds providing a lead source, a tin source or a germanium source, organic/inorganic halides and a solvent capable of dissolving the compounds to prepare a precursor solution with the concentration of 0.5-2.5 mol/L.
The metal compound providing the source of lead is lead chloride (PbCl)2) Lead bromide (PbBr)2) Lead iodide (PbI)2) Or lead acetate (Pb (CH)3COO)2·xH2O); the metal compound for providing the tin source is stannous chloride (SnCl)2) Tin tetrachloride (SnCl)4) Stannous bromide (SnBr)2) Or tin iodide (SnI)2) (ii) a The metal compound for providing the germanium source is germanium chloride (GeCl)2) Germanium bromide (GeBr)2) Or germanium iodide (GeI)2)。
The solvent is at least one of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
Step 4, growing the perovskite single crystal with the surface light trapping structure: and transferring the template and the prepared precursor single crystal growth liquid to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 40-120 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain large-size single crystal.
Step 5, taking out ABX from the container3Perovskite crystal: the surface structure of the perovskite crystal is rapidly damaged due to the residual growth solution. Therefore, under the condition of maintaining the single crystal growth temperature, the residual solution needs to be taken out quickly with care to ensure that no residual solution exists in the system. And finally cooling to room temperature, and taking the single crystal from the surface of the template. Thereby obtaining a perovskite single crystal having a surface light trapping structure opposite to the surface structure of the template, as shown in FIG. 2.
Example 1
Step 1, cleaning monocrystalline silicon with a pyramid structure with the surface average diameter of 1 mu m: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1 diluted in 3-aminopropyltrimethoxysilane, and activated at 60 ℃ for 20 minutes.
Step 3, preparing a precursor single crystal growth solution: weighing CH with the stoichiometric ratio of 1:13NH3I and PbI2Dissolved in 20mL of gamma-butyrolactone to obtain 1.23mol/L clear and transparent CH3NH3PbI3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 95 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking CH out of the container3NH3PbI3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 95 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 2
Step 1, cleaning monocrystalline silicon with a pyramid structure with the surface average diameter of 10 mu m: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1, and then activating the mixture at 50 ℃ for 40 minutes in 3-aminopropyltriethoxysilane.
Step 3, preparing a precursor single crystal growth solution: weighing CH with the stoichiometric ratio of 1:13NH3Br and PbBr2Dissolving in 20ml N dimethyl formamide to obtain clear and transparent CH of 1.5mol/L3NH3PbBr3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 50 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking CH out of the container3NH3PbBr3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 50 ℃. Finally cooling to room temperature, and taking the single crystal from the surface of the template。
Example 3
Step 1, cleaning monocrystalline silicon with a pyramid structure with the surface average diameter of 5 mu m: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1 into mercaptopropyltrimethoxysilane, the activation treatment was carried out at 70 ℃ for 40 minutes.
Step 3, preparing a precursor single crystal growth solution: weighing CH with the stoichiometric ratio of 1:13NH3Cl and PbCl2Dissolved in 20mL of dimethyl sulfoxide to obtain 2.5mol/L clear and transparent CH3NH3PbCl3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, raising the temperature to 75 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking CH out of the container3NH3PbCl3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 75 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 4
Step 1, cleaning monocrystalline silicon with an inverted pyramid structure with the surface average diameter of 10 mu m: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1 into mercaptopropyltrimethoxysilane, and activating at 60 ℃ for 60 minutes.
Step 3, preparing a precursor single crystal growth solution: weighing H with the stoichiometric ratio of 1:12N-CH＝NH2I and GeI2Dissolved in 20mL of gamma-butyrolactone to obtain 1.1mol/L clear and transparent H2N-CH＝NH2GeI3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 90 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking out H from the container2N-CH＝NH2GeI3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 90 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 5
Step 1, cleaning stainless steel with an inverted pyramid structure with the surface average diameter of 20 μm: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1 diluted in 3-aminopropyltrimethoxysilane, and activated at 60 ℃ for 20 minutes.
Step 3, preparing a precursor single crystal growth solution: weighing H with the stoichiometric ratio of 1:12N-CH＝NH2Br and PbBr2Dissolved in 20ml of N-dimethylformamide to give 1.5mol/L of clear and transparent H2N-CH＝NH2PbBr3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 95 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking out H from the container2N-CH＝NH2PbBr3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 95 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 6
Step 1, cleaning stainless steel with an inverted pyramid structure with the surface average diameter of 150 μm: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1 diluted in 3-aminopropyltrimethoxysilane, and activated at 60 ℃ for 20 minutes.
Step 3, preparing a precursor single crystal growth solution: weighing CsBr and PbBr with the stoichiometric ratio of 1:12Dissolving in 20mL of N, N-dimethylformamide to obtain 0.8mol/L clear and transparent CsPbBr3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 70 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking out CsPbBr from the container3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 70 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 7
Step 1, cleaning stainless steel with a concave hemispherical structure with the surface average diameter of 50 μm: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1, and then activating the mixture at 50 ℃ for 40 minutes in 3-aminopropyltriethoxysilane.
Step 3, preparing a precursor single crystal growth solution: weighing CH with the stoichiometric ratio of 1:13NH3Br and PbBr2Dissolving in 20mL of N, N-dimethylformamide to obtain 1.8mol/L clear and transparent CH3NH3PbBr3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, raising the temperature to 40 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking CH out of the container3NH3PbBr3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 40 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 8
Step 1, cleaning stainless steel with an inverted pyramid structure with the surface average diameter of 20 μm: and ultrasonically cleaning the mixture for 15 minutes by using acetone, isopropanol and ultrapure water respectively.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1, and then activating the mixture at 50 ℃ for 40 minutes in 3-aminopropyltriethoxysilane.
Step 3, preparing a precursor single crystal growth solution: weighing CH with the stoichiometric ratio of 1:13NH3I and PbI2Dissolved in 20mL of gamma-butyrolactone to obtain 1.2mol/L clear and transparent CH3NH3PbI3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 90 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking CH out of the container3NH3PbI3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 90 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 9
Step 1, washing Polystyrene (PS) microplates with a surface average diameter of 20 nm: ultrasonic cleaning in ethanol for 15 minutes.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1, and then activating the mixture at 50 ℃ for 10 minutes in 3-aminopropyltriethoxysilane.
Step 3, preparing a precursor single crystal growth solution: weighing CH with the stoichiometric ratio of 1:13NH3I and PbI2Dissolved in 20mL of gamma-butyrolactone to obtain 0.5mol/L clear and transparent CH3NH3PbI3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 120 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking CH out of the container3NH3PbI3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 120 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.
Example 10
Step 1, washing Polystyrene (PS) microplates with a surface average diameter of 6000 nm: ultrasonic cleaning in ethanol for 15 minutes.
Step 2, carrying out surface modification treatment on the template: the single crystal silicon wafer was placed in a container containing chlorobenzene 10: 1, and then activating the mixture at 60 ℃ for 10 minutes in 3-aminopropyltriethoxysilane.
Step 3, preparing a precursor single crystal growth solution: weighing CH with the stoichiometric ratio of 1:13NH3I and SnI2Dissolved in 20mL of gamma-butyrolactone to obtain 0.6mol/L clear and transparent CH3NH3SnI3And (4) precursor growth liquid.
Step 4, growing the perovskite single crystal with the surface light trapping structure: the template and the prepared precursor liquid are transferred to a closed container. And (3) placing the reaction container system in a heating blast drying oven, heating to 80 ℃, and after a period of time, allowing seed crystals to appear on the surface of the template with the light trapping structure in the container and grow gradually to obtain the monocrystal with larger size.
Step 5, taking CH out of the container3NH3SnI3Crystal: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 80 ℃. And finally cooling to room temperature, and taking the single crystal from the surface of the template.

Claims (6)

1. The preparation method of the perovskite single crystal with the light trapping structure is characterized in that a template with the light trapping structure on the surface is placed in ABX3In the perovskite precursor solution, the precursor solution performs heterogeneous nucleation on the surface of a template with a light trapping structure, and then ABX with the surface light trapping structure opposite to the surface light trapping structure of the template is grown in situ3A perovskite single crystal;
before growing a single crystal on a template, carrying out activation treatment on the template, placing the template in a silane coupling agent with amino or sulfhydryl groups, and carrying out activation treatment for 10-60 minutes at the temperature of 50-70 ℃, so as to obtain a chemical group capable of simultaneously connecting the template and perovskite on the surface of the template;
growing ABX on the surface in situ3Template of perovskite single crystal from ABX3Taking out the perovskite precursor solution, maintaining the growth temperature of the single crystal until no residual ABX is left on the surface3Cooling the perovskite precursor solution, separating the single crystal from the surface of the template, ABX3The separation surface of the perovskite single crystal forms a surface light trapping structure opposite to the surface light trapping structure of the template;
the ABX3In the perovskite, A is CH3NH3 +、H2N-CH=NH2 +、(CH3)4N+、C7H7 +、Cs+Or C3H11SN3 2+(ii) a B is Pb, Ge or Sn; x is Cl, Br or I;
the light trapping structure on the surface of the template is a rugged structure which is a plurality of repeated unit structures.
2. The method for preparing a perovskite single crystal with a light trapping structure according to claim 1, wherein the unit structure is a pyramid, an inverted pyramid, a spherical or hemispherical concave hole structure, and the diameter of the unit structure is 20nm-150 μm.
3. The method for preparing a perovskite single crystal having a light trapping structure according to claim 1, wherein the perovskite single crystal is prepared according to ABX3Weighing halide containing A and a metal compound capable of providing a B source according to the stoichiometric ratio of the perovskite single crystal, and dissolving the halide and the metal compound in a solvent to obtain ABX with the concentration of 0.5-2.5 mol/L3A perovskite precursor solution.
4. The method for preparing a perovskite single crystal having a light trapping structure as claimed in claim 3, wherein the metal compound providing a lead source is lead chloride (PbCl)2) Lead bromide (PbBr)2) Lead iodide (PbI)2) Or lead acetate (Pb (CH)3COO)2·xH2O)；
The metal compound for providing the tin source is stannous chloride (SnCl)2) Tin tetrachloride (SnCl)4) Stannous bromide (SnBr)2) Or tin iodide (SnI)2)；
The metal compound for providing the germanium source is germanium chloride (GeCl)2) Germanium bromide (GeBr)2) Or germanium iodide (GeI)2)；
The solvent is at least one of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
5. The method for preparing a perovskite single crystal having a light trapping structure according to claim 1, wherein ABX3When the perovskite precursor solution is used for single crystal growth on the template, the sealing is carried out, and the growth temperature is 40-120 ℃.
6. A perovskite single crystal having a light trapping structure obtained by the production method according to any one of claims 1 to 5.
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