CN110541187A - 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 PDFInfo
- Publication number
- CN110541187A CN110541187A CN201910959359.4A CN201910959359A CN110541187A CN 110541187 A CN110541187 A CN 110541187A CN 201910959359 A CN201910959359 A CN 201910959359A CN 110541187 A CN110541187 A CN 110541187A
- Authority
- CN
- China
- Prior art keywords
- single crystal
- template
- light trapping
- trapping structure
- perovskite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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 high light trapping structure quality. The preparation method comprises the steps of putting a template with a light trapping structure on the surface into an ABX3 perovskite precursor solution after activation treatment, carrying out heterogeneous nucleation on the surface of the template with the light trapping structure by the precursor solution, and further growing an ABX3 perovskite single crystal with a surface light trapping structure opposite to the light trapping structure on the surface of the template in situ; wherein, A is CH3NH3+, H2N-CH ═ NH2+, (CH3)4N +, C7H7+, Cs + or C3H11SN32 +; 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
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 preparation method of a perovskite single crystal with a light trapping structure comprises the steps of putting a template with the light trapping structure on the surface into an ABX3 perovskite precursor solution after activation treatment, carrying out heterogeneous nucleation on the surface of the template with the light trapping structure by the precursor solution, and further growing an ABX3 perovskite single crystal with a surface light trapping structure opposite to the light trapping structure on the surface of the template in situ; wherein, A is CH3NH3+, H2N-CH ═ NH2+, (CH3)4N +, C7H7+, Cs + or C3H11SN32 +; 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 the stoichiometric ratio of the ABX3 perovskite single crystal, a halide containing A and a metal compound capable of providing a B source are weighed and dissolved in a solvent to obtain an ABX3 perovskite precursor solution with the concentration of 0.5-2.5 mol/L.
Further, the metal compound providing a lead source is lead chloride (PbCl2), lead bromide (PbBr2), lead iodide (PbI2), or lead acetate (Pb (CH3COO) 2. xH 2O);
The metal compound for providing the tin source is stannous chloride (SnCl2), stannic chloride (SnCl4), stannous bromide (SnBr2) or stannic iodide (SnI 2);
The metal compound providing the germanium source is germanium chloride (GeCl2), germanium bromide (GeBr2) or germanium iodide (GeI 2);
The solvent is at least one of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
Preferably, when the single crystal growth of the ABX3 perovskite precursor solution is carried out on the template, the sealing and the growth temperature are 40-120 ℃.
Preferably, the template with the ABX3 perovskite single crystal grown in situ on the surface is taken out from the ABX3 perovskite precursor solution, the single crystal growth temperature is kept until no ABX3 perovskite precursor solution remains on the surface, the single crystal is separated from the surface of the template, and the separation surface of the ABX3 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 for obtaining the ABX3 perovskite single crystal with the surface light trapping structure by in-situ growth of the template has the advantages of simple process, mild growth conditions, low equipment requirement and strong operability. 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).
According to the invention, a material with an optimized light trapping structure on the surface is added into a reaction system to serve as a hard template, and then a fresh ABX3 perovskite precursor solution is added into the system, so that a perovskite single crystal with a surface light trapping structure opposite to that of the template structure is grown on the surface of the template in situ. Specifically, a template with a light trapping structure on the surface is activated and then placed into an ABX3 perovskite precursor solution, the precursor solution performs heterogeneous nucleation on the surface of the template with the light trapping structure, and then an ABX3 perovskite single crystal with a surface light trapping structure opposite to the light trapping structure on the surface of the template is grown in situ; wherein, A is CH3NH3+, H2N-CH ═ NH2+, (CH3)4N +, C7H7+, Cs + or C3H11SN32 +; 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.
The ABX3 perovskite single crystal with the surface light trapping structure is obtained by the method, wherein A is CH3NH3+, H2N-CH ═ NH2+, (CH3)4N +, C7H7+, Cs + or C3H11SN32 +; b is Pb2+, Ge2+ or Sn2 +; 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.
The growth method of the ABX3 perovskite single crystal with the surface light trapping structure, as shown in figure 1, comprises the following specific steps:
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 organic/inorganic halide and a compound capable of providing a metal source in a stoichiometric ratio, and dissolving the organic/inorganic halide and the compound in a solvent to obtain a clear and transparent ABX3 perovskite single crystal precursor single crystal growth solution.
The perovskite single crystal precursor solution may be of the ABX3 type, wherein a is CH3NH3+, H2N-CH ═ NH2+, (CH3)4N +, C7H7+, Cs +, or C3H11SN32 +; 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 lead source is lead chloride (PbCl2), lead bromide (PbBr2), lead iodide (PbI2) or lead acetate (Pb (CH3COO) 2. xH 2O); the metal compound for providing the tin source is stannous chloride (SnCl2), stannic chloride (SnCl4), stannous bromide (SnBr2) or stannic iodide (SnI 2); the metal compound providing the germanium source is germanium chloride (GeCl2), germanium bromide (GeBr2), 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 ABX3 perovskite crystals from the container: 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: CH3NH3I and PbI2 in a stoichiometric ratio of 1:1 are weighed and dissolved in 20mL of gamma-butyrolactone to obtain 1.23mol/L clear and transparent CH3NH3PbI3 precursor growth solution.
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.
And 5, taking the CH3NH3PbI3 crystal out of the container: 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 CH3NH3Br and PbBr2 in a stoichiometric ratio of 1:1, and dissolving in 20mLN, N-dimethylformamide to obtain 1.5mol/L clear and transparent CH3NH3PbBr3 precursor growth solution.
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.
And 5, taking out CH3NH3PbBr3 crystals from the container: the residual solution was carefully and quickly removed while maintaining an ambient temperature of 50 ℃. And 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: CH3NH3Cl and PbCl2 in a stoichiometric ratio of 1:1 are weighed and dissolved in 20mL of dimethyl sulfoxide to obtain 2.5mol/L clear and transparent CH3NH3PbCl3 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.
And 5, taking out CH3NH3PbCl3 crystals from the container: 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: H2N-CH-NH 2I and GeI2 with the stoichiometric ratio of 1:1 are weighed and dissolved in 20mL of gamma-butyrolactone to obtain 1.1mol/L clear and transparent H2N-CH-NH 2GeI3 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 H2N-CH ═ NH2GeI3 crystals from the vessel: 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: H2N-CH-NH 2Br and PbBr2 in a stoichiometric ratio of 1:1 are weighed and dissolved in 20mLN, N-dimethylformamide to obtain 1.5mol/L clear and transparent H2N-CH-NH 2PbBr3 precursor growth solution.
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 the H2N-CH ═ NH2PbBr3 crystals from the vessel: 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 PbBr2 with the stoichiometric ratio of 1:1, and dissolving the CsBr and PbBr2 in 20mL of N, N-dimethylformamide to obtain 0.8mol/L of clear and transparent CsPbBr3 precursor growth solution.
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 CsPbBr3 crystal from the container: 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 CH3NH3Br and PbBr2 in a stoichiometric ratio of 1:1, and dissolving in 20mL of N, N dimethylformamide to obtain 1.8mol/L clear and transparent CH3NH3PbBr3 precursor growth solution.
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.
And 5, taking out CH3NH3PbBr3 crystals from the container: 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: CH3NH3I and PbI2 in a stoichiometric ratio of 1:1 are weighed and dissolved in 20mL of gamma-butyrolactone to obtain 1.2mol/L of clear and transparent CH3NH3PbI3 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.
And 5, taking the CH3NH3PbI3 crystal out of the container: 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: CH3NH3I and PbI2 in a stoichiometric ratio of 1:1 are weighed and dissolved in 20mL of gamma-butyrolactone to obtain 0.5mol/L clear and transparent CH3NH3PbI3 precursor growth solution.
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.
And 5, taking the CH3NH3PbI3 crystal out of the container: 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 CH3NH3I and SnI2 with the stoichiometric ratio of 1:1, and dissolving in 20mL of gamma-butyrolactone to obtain 0.6mol/L clear and transparent CH3NH3SnI3 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.
And 5, taking out the CH3NH3SnI3 crystal from the container: 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 (10)
1. A preparation method of a perovskite single crystal with a light trapping structure is characterized in that a template with the light trapping structure on the surface is placed in an ABX3 perovskite precursor solution, and then the ABX3 perovskite single crystal with the surface light trapping structure opposite to the light trapping structure on the surface of the template is grown in situ.
2. The method for preparing a perovskite single crystal having a light trapping structure according to claim 1, wherein in the ABX3 perovskite, a is CH3NH3+, H2N-CH ═ NH2+, (CH3)4N +, C7H7+, Cs + or C3H11SN32 +; b is Pb, Ge or Sn; x is Cl, Br or I.
3. the method according to claim 1, wherein the light-trapping structure on the surface of the template is a rugged structure, and the rugged structure is a plurality of repeating unit structures.
4. The method for preparing a perovskite single crystal with a light trapping structure according to claim 3, 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.
5. The method for preparing a perovskite single crystal with a light trapping structure according to claim 1, wherein before growing the single crystal on the template, the template is subjected to activation treatment, the template is placed in a silane coupling agent with amino or mercapto groups, and the activation treatment is carried out at a temperature of 50-70 ℃ for 10-60 minutes, so that chemical groups capable of simultaneously connecting the template and the perovskite are obtained on the surface of the template.
6. The method for preparing a perovskite single crystal with a light trapping structure as claimed in claim 1, wherein a halide containing A and a metal compound capable of providing a B source are weighed according to the stoichiometric ratio of the ABX3 perovskite single crystal and dissolved in a solvent to obtain an ABX3 perovskite precursor solution with a concentration of 0.5-2.5 mol/L.
7. the method of claim 6, wherein the metal compound providing a lead source is lead chloride (PbCl2), lead bromide (PbBr2), lead iodide (PbI2) or lead acetate (Pb (CH3COO) 2. xH 2O);
The metal compound for providing the tin source is stannous chloride (SnCl2), stannic chloride (SnCl4), stannous bromide (SnBr2) or stannic iodide (SnI 2);
The metal compound providing the germanium source is germanium chloride (GeCl2), germanium bromide (GeBr2) or germanium iodide (GeI 2);
The solvent is at least one of gamma-butyrolactone, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone.
8. The method for preparing a perovskite single crystal with a light trapping structure according to claim 1, wherein the ABX3 perovskite precursor solution is sealed and grown at a temperature of 40 ℃ to 120 ℃ when the single crystal is grown on a template.
9. The method for preparing a perovskite single crystal with a light trapping structure as claimed in claim 1, wherein the template with the ABX3 perovskite single crystal grown in situ on the surface is taken out from the ABX3 perovskite precursor solution, the growth temperature of the single crystal is kept until no ABX3 perovskite precursor solution remains on the surface, the single crystal is cooled and separated from the surface of the template, and the separation surface of the ABX3 perovskite single crystal forms a surface light trapping structure opposite to the light trapping structure on the surface of the template.
10. A perovskite single crystal having a light trapping structure prepared by the method of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910959359.4A CN110541187B (en) | 2019-10-10 | 2019-10-10 | Perovskite single crystal with light trapping structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910959359.4A CN110541187B (en) | 2019-10-10 | 2019-10-10 | Perovskite single crystal with light trapping structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110541187A true CN110541187A (en) | 2019-12-06 |
| CN110541187B CN110541187B (en) | 2021-09-07 |
Family
ID=68715634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910959359.4A Active CN110541187B (en) | 2019-10-10 | 2019-10-10 | Perovskite single crystal with light trapping structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110541187B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057221A (en) * | 2021-12-20 | 2022-02-18 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing flower-like lead halide cesium perovskite structure nanowire |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911705A (en) * | 2015-05-18 | 2015-09-16 | 陕西师范大学 | Method for growing ABX3 perovskite single crystals in low-temperature solution |
| CN105762286A (en) * | 2016-02-26 | 2016-07-13 | 上海科技大学 | Methods for preparing perovskite thin film of inverse opal structure and corresponding solar cell |
| US20170226641A1 (en) * | 2014-08-07 | 2017-08-10 | Okinawa Institute Of Science And Technology School Corporation | System and method based on multi-source deposition for fabricating perovskite film |
| CN107068865A (en) * | 2016-12-12 | 2017-08-18 | 苏州大学 | A kind of perovskite solar cell and preparation method thereof |
| CN107316940A (en) * | 2017-06-01 | 2017-11-03 | 苏州大学 | Preparation method with the adjusted and controlled perovskite thin film of light and optics |
| CN107591483A (en) * | 2017-08-22 | 2018-01-16 | 电子科技大学 | A kind of perovskite solar cell for mixing light trapping structure and preparation method thereof |
| CN109148697A (en) * | 2018-09-21 | 2019-01-04 | 北京恒信卓元科技有限公司 | A kind of preparation method of perovskite solar battery |
-
2019
- 2019-10-10 CN CN201910959359.4A patent/CN110541187B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170226641A1 (en) * | 2014-08-07 | 2017-08-10 | Okinawa Institute Of Science And Technology School Corporation | System and method based on multi-source deposition for fabricating perovskite film |
| CN104911705A (en) * | 2015-05-18 | 2015-09-16 | 陕西师范大学 | Method for growing ABX3 perovskite single crystals in low-temperature solution |
| CN105762286A (en) * | 2016-02-26 | 2016-07-13 | 上海科技大学 | Methods for preparing perovskite thin film of inverse opal structure and corresponding solar cell |
| CN107068865A (en) * | 2016-12-12 | 2017-08-18 | 苏州大学 | A kind of perovskite solar cell and preparation method thereof |
| CN107316940A (en) * | 2017-06-01 | 2017-11-03 | 苏州大学 | Preparation method with the adjusted and controlled perovskite thin film of light and optics |
| CN107591483A (en) * | 2017-08-22 | 2018-01-16 | 电子科技大学 | A kind of perovskite solar cell for mixing light trapping structure and preparation method thereof |
| CN109148697A (en) * | 2018-09-21 | 2019-01-04 | 北京恒信卓元科技有限公司 | A kind of preparation method of perovskite solar battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057221A (en) * | 2021-12-20 | 2022-02-18 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing flower-like lead halide cesium perovskite structure nanowire |
| CN114057221B (en) * | 2021-12-20 | 2023-06-13 | 中国科学院长春光学精密机械与物理研究所 | Method for preparing flower-like lead halide cesium perovskite structure nanowire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110541187B (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106245114B (en) | A kind of growth form in the micro- reaction system of Flowing liquid and the controllable ultra-thin ABX of thickness3The method of perovskite monocrystalline thin slice | |
| CN105951168B (en) | Large area ABX3Type perovskite crystal film growth method and device | |
| CN108666428B (en) | Perovskite single crystal thin film solar cell preparation method and device | |
| CN105586641B (en) | Methylamine lead halide phosphate compounds monocrystalline micro flakes growing method and grower | |
| CN107325812A (en) | A kind of perovskite structure luminescent material and its production method based on anti-solvent | |
| CN106757342A (en) | A kind of anti-solvent diffusion growth ABX3The method of perovskite monocrystalline | |
| Kahraman et al. | Effects of the sulfurization temperature on sol gel-processed Cu2ZnSnS4 thin films | |
| CN106676631A (en) | Method for preparing ABX3 perovskite single crystal film | |
| CN111554760B (en) | Precursor solution of copper-zinc-tin-sulfur thin film solar cell and preparation method and application thereof | |
| CN105405979A (en) | Preparation method of organic and inorganic hybrid perovskite single crystal | |
| CN108950675B (en) | Organic-inorganic hybrid perovskite single crystal preparation method based on two-phase method | |
| CN109560197B (en) | Ferroelectric perovskite solar cell based on polarization and preparation method thereof | |
| CN110541187B (en) | Perovskite single crystal with light trapping structure and preparation method thereof | |
| CN105810831A (en) | Lead-tin hybrid perovskite thin film, and preparation method and application therefor | |
| CN105161555B (en) | Single-crystal particle film and preparation method of substrate-free flexible solar cell employing single-crystal particle film | |
| CN107093671A (en) | The preparation method of monocrystalline perovskite organic metal halide film | |
| JP2007242646A (en) | Method of forming buffer layer and thin-film solar cell therewith | |
| CN104264211B (en) | High temperature solvent thermal preparation method and applications of monocrystalline submicron Cu2ZnSnS4 particle | |
| CN111029466B (en) | Perovskite solar cell without carrier transport layer and preparation method thereof | |
| CN113451515A (en) | Preparation method of perovskite solar cell with GaN semiconductor material as double functional layers | |
| CN109686846A (en) | A kind of modifying interface method of organic metal halide perovskite solar cell | |
| CN115353293B (en) | Preparation method of perovskite film grown by vertical orientation crystallization | |
| CN113097317B (en) | Germanium selenide or germanium sulfide polycrystalline film and preparation method and application thereof | |
| CN107180914A (en) | A kind of preparation method of perovskite thin film battery | |
| CN112210816B (en) | Perovskite single crystal sheet, method for promoting growth of perovskite single crystal sheet and application of perovskite single crystal sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |