CN108023017B - Single crystal film of organic-inorganic composite perovskite material and preparation method and application thereof - Google Patents

Single crystal film of organic-inorganic composite perovskite material and preparation method and application thereof Download PDF

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CN108023017B
CN108023017B CN201610964168.3A CN201610964168A CN108023017B CN 108023017 B CN108023017 B CN 108023017B CN 201610964168 A CN201610964168 A CN 201610964168A CN 108023017 B CN108023017 B CN 108023017B
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single crystal
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CN108023017A (en
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胡劲松
陈尧轩
万立骏
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Institute of Chemistry CAS
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a single crystal film of an organic-inorganic composite perovskite material, a preparation method and application thereof, wherein the method is to use a two-dimensional limited-domain induced solution to prepare the single crystal film of the organic-inorganic composite large-area perovskite, and the method is used for ABX3The perovskite structure material is effective, and the single crystal thin film of the perovskite material with high quality and large area can be obtained. The thickness of the film is adjustable within the range of 10 nanometers to 10 micrometers, and the film can meet the thickness requirements of different photoelectric devices on the light absorption layer. The film can be prepared on different substrates, and the in-situ growth method ensures that the single crystal film has good contact with a base, and can adapt to the interface requirements of different photoelectric devices on the light absorption layer. The preparation method has the advantages of mild preparation conditions, simple steps, convenience in operation, low cost, low energy consumption and the like, and is suitable for large-scale industrial production application of photoelectric devices with different purposes.

Description

Single crystal film of organic-inorganic composite perovskite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a single crystal film of an organic-inorganic composite perovskite material, and a preparation method and application thereof.
Background
In recent years, organic-inorganic composite perovskite materials are widely concerned due to excellent photoelectric properties, and thin film solar cells based on the materials break through frequently in efficiency in short years, rapidly increase from less than 4% in 2009 to 22.1% in NREL certification in recent years, and exceed the efficiency record of polycrystalline silicon cells. Since the perovskite cell has low cost and simple preparation process, the perovskite cell is considered to be one of powerful competitors of the next generation solar cell. In addition, the perovskite material has excellent photoelectric properties, so that the perovskite material has great application prospects in the aspects of laser, light-emitting diodes, photoelectric sensors and the like.
The typical structural formula of the perovskite type material is ABX3Wherein A is typically CH3NH3 +、CH3CH2NH3 +、NH2CH＝NH2 +And as a substitute element Cs for the all-inorganic perovskite material+(ii) a B is usually Pb2+、Sn2+、Ge2+And X is a halogen ion. The material with the structure has the advantages of rich raw materials, low price, easy synthesis and the like, and simultaneously the ABX is prepared from the ABX3The organic-inorganic composite perovskite material with the structure has excellent photoelectric properties such as good crystallinity, high light absorption coefficient, good bipolar semiconductor performance, high carrier mobility, long carrier recombination life and the like.
In order to explore the performance limit and action mechanism of perovskite material and to prepare better devices, research on single crystal of perovskite material is also receiving attention, only 3 papers on the study of single crystal growth and performance of perovskite material were published in Huang, Sargent, Yang et al in 2015, and many papers on the synthesis and application of perovskite material crystal growth were published in other journals with great influence. At present, research on perovskite material single crystals is mainly focused on research on perovskite bulk crystals and various forms of nano crystals, perovskite bulk single crystals have been proved to have excellent photoelectric properties such as low defect state density, high carrier mobility, long carrier recombination life and the like, but because of the extremely strong crystallization property, a two-dimensional single crystal thin film is difficult to grow by a conventional single crystal growth method, so that research on two-dimensional thin film perovskite single crystals has not been achieved too much.
Up to now, the processes for preparing the light absorption layer of the perovskite photoelectric device mainly comprise spin coating, spray coating, blade coating, double-source thermal evaporation and the like. The perovskite photoelectric device light absorption layer prepared by various process methods is a perovskite polycrystalline film, and the density of trap state energy level is increased due to the inevitable existence of a large number of crystal grain boundaries and surface defects of the polycrystalline film, so that the reduction of important parameters such as carrier mobility, service life and diffusion length is caused, and the performance of the photoelectric device is further reduced. Therefore, in order to further improve the performance of the perovskite photoelectric device, a perovskite single crystal thin film with high quality, large area, mild preparation conditions and high controllability needs to be prepared.
Disclosure of Invention
The invention aims to provide a preparation method of a single crystal thin film of an organic-inorganic composite perovskite material. The preparation method is used for preparing the single crystal film of the organic-inorganic composite perovskite material in a two-dimensional limited-domain induced growth mode, and has the advantages of simplicity, low cost, low energy consumption, convenience in operation and the like.
The invention also aims to provide the single crystal film of the organic-inorganic composite perovskite material prepared by the preparation method, the single crystal film has the characteristics of high quality, large area, high controllability and the like, the thickness of the single crystal film can be controllably adjusted within a certain range, the single crystal film has no selectivity on a prepared substrate, and the single crystal film can meet the preparation requirements of various photoelectric devices.
The invention also aims to provide application of the single crystal thin film of the organic-inorganic composite perovskite material, which can be suitable for large-scale industrial production application of photoelectric devices (particularly solar cells).
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a single crystal thin film of an organic-inorganic composite perovskite material comprises the following steps:
(1) preparing a precursor solution of an organic-inorganic composite perovskite material, and treating a substrate to be used for growing a monocrystalline film;
(2) combining the substrates obtained by the treatment in the step (1) into a two-dimensional confinement structure, contacting the two-dimensional confinement structure with a precursor solution of the perovskite material, and forming a thin film of the precursor solution through capillary action;
(3) under certain conditions, the precursor grows into single crystal in situ to obtain the single crystal film of the organic-inorganic composite perovskite material.
According to the present invention, the preparation method further comprises the steps of:
(4) and (4) removing the precursor solvent in the single crystal film of the organic-inorganic composite perovskite material prepared in the step (3) to obtain the final single crystal film of the organic-inorganic composite perovskite material.
According to the invention, in step (1), the precursor of the organic-inorganic composite perovskite material comprises at least one compound with the structural formula AX and at least one compound with the structural formula BX2Wherein A is selected from CH3NH3 +，CH3CH2NH3 +，NH2CH＝NH2 +，CH3(CH2)2NH3 +，CH3(CH2)3NH3 +，C6H5(CH2)2NH3 +One or a mixture thereof; b is selected from Pb2+，Sn2 +，Ge2+One or a mixture thereof; x is selected from Cl-，Br-，I-Or a mixture thereof.
According to the invention, in step (1), the compound of formula AX is reacted with a compound of formula BX2The molar ratio of the compound (1) to the compound (10) is 1:1 to 10, preferably 1:1 to 3.
According to the present invention, in the step (1), the solvent of the precursor solution is selected from one or more of tetrahydrofuran, gamma-butyrolactone (GBL), acetonitrile, aniline, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), etc.; preferably one or more of gamma-butyrolactone (GBL), dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF).
According to the invention, in the step (1), the concentration of the precursor solution can be 0.01-5 mol/L, preferably 0.5-2.5 mol/L.
According to the invention, in the step (1), the substrate for growing the single crystal thin film includes, but is not limited to, a silicon wafer, a quartz wafer, a glass wafer, a high molecular Polymer (PET) substrate, an Indium Tin Oxide (ITO) wafer, a fluorine-doped tin dioxide (FTO) wafer, a graphene substrate, a mica wafer, various metal substrates, and the like.
According to the invention, in step (2), the substrates can be combined in any manner into a two-dimensional domain-restricted structure.
According to the invention, in the step (2), the substrate is contacted with the precursor solution in a manner including, but not limited to, infiltrating the precursor solution into the two-dimensional confinement structure combined by the substrate in a dropwise manner to form the precursor solution thin film; or putting the substrate partially or completely into the precursor solution to form the precursor solution film.
According to the invention, in the step (3), the temperature of in-situ growth can be 0-200 ℃, preferably 50-150 ℃, and more preferably 80-110 ℃.
According to the invention, in step (3), the in-situ growth time is 6 h-5 d, preferably 24 h-48 h.
According to the invention, in the step (3), the thickness of the single crystal thin film can be regulated by the pressure applied on the substrate.
Preferably, the thickness of the single crystal thin film decreases nonlinearly with increasing pressure applied to the substrate, for example, when the pressure is greater than 1kPa, the single crystal thin film can be formed; when the pressure is more than 200kPa, the thickness of the single crystal film can reach the nanometer level, the accurate measurement is difficult when the pressure is increased continuously, and the thickness of the single crystal film can reach 10nm after the pressure is increased to the maximum.
According to the invention, in step (3), the organic-inorganic composite perovskite material comprises at least one material with a structural formula ABX3Wherein A is selected from CH3NH3 +，CH3CH2NH3 +，NH2CH＝NH2 +，CH3(CH2)2NH3 +，CH3(CH2)3NH3 +，C6H5(CH2)2NH3 +One or a mixture thereof; b is selected from Pb2+，Sn2+，Ge2+One or a mixture thereof; x is selected from Cl-，Br-，I-Or a mixture thereof.
According to the invention, in the step (4), the precursor solvent in the monocrystalline film can be removed by one or more of a hot stage, an oven, a dry box baking and the like.
According to the invention, in the step (4), the removal time of the precursor solvent can be 12 h-5 d depending on the perovskite component; the removal temperature of the precursor solvent can be 50-150 ℃, and preferably 80-110 ℃.
The invention also provides a monocrystalline film of the organic-inorganic composite perovskite material prepared by the method, wherein the thickness of the monocrystalline film is adjustable between micron level and nanometer level, namely the thickness of the monocrystalline film is adjustable within the range of 10 nanometers to 10 microns, and the film thickness is uniform.
According to the invention, the prepared organic-inorganic composite perovskite material has the advantages of high quality of the single crystal film, large area (the diameter and the length of the area of the film are at least 500 mu m), controllable thickness and no selectivity to a substrate. The substrate for growing the single crystal thin film includes, but is not limited to, a silicon wafer, a quartz wafer, a glass wafer, a high molecular Polymer (PET) substrate, an Indium Tin Oxide (ITO) wafer, a fluorine-doped tin dioxide (FTO) wafer, a graphene substrate, a mica wafer, various metal substrates, and the like.
In the invention, the prepared single crystal film of the organic-inorganic composite perovskite material has few crystal defects and high quality, and the photoelectric property of the film is equivalent to that of a bulk phase single crystal of a corresponding perovskite material.
The invention also provides application of the single crystal film of the organic-inorganic composite perovskite material, which can be suitable for large-scale industrial production and application of photoelectric devices, particularly solar cells.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a single crystal film of an organic-inorganic composite perovskite material, which is characterized in that a two-dimensional limited domain induction solution is utilized to prepare the single crystal film of the organic-inorganic composite large-area perovskite, and the method is used for preparing the ABX3The perovskite structure materials are all effective, and single crystal thin films of perovskite materials with high quality and large area (such as the area diameter and the length of the thin film are at least 500 mu m) can be obtained. The preparation method has mild preparation conditions, andsimple preparation steps, convenient operation, low cost, low energy consumption and the like, and is suitable for industrial production.
2. The invention also provides the monocrystalline film of the organic-inorganic composite perovskite material prepared by the method, the thickness of the monocrystalline film of the organic-inorganic composite perovskite material is adjustable within the range of 10 nanometers to 10 micrometers, and the thickness of the monocrystalline film can meet the thickness requirements of different photoelectric devices on light absorption layers. The single crystal film of the organic-inorganic composite perovskite material can be prepared on different substrates, and the in-situ growth method ensures that the single crystal film and the substrate have good contact, and can meet the interface requirements of different photoelectric devices on light absorption layers. The single crystal film of the organic-inorganic composite perovskite material has extremely high crystal quality, and tests prove that the single crystal film has photoelectric properties equivalent to those of perovskite bulk single crystals, and can meet the requirements of photoelectric devices on single crystal material light absorption layers. The single crystal film of the organic-inorganic composite perovskite material has good stability, does not change obviously after being placed in the air with the atmospheric pressure of 1, the normal temperature and the humidity of 20 percent for 5 months, can greatly improve the service life of a photoelectric device and reduce the preparation cost of the device.
3. The invention also provides the application of the single crystal film of the organic-inorganic composite perovskite material, which is used for the large-scale industrial production application of photoelectric devices with different applications.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a single crystal thin film of the organic-inorganic composite perovskite material prepared in example 1.
FIG. 2 shows MABr powder (wherein MA is measured under a standard XRD light source) of a single crystal thin film of an organic-inorganic composite perovskite material prepared in example 1+Is CH3NH3 +)、PbBr2Powder and MAPbBr3Single crystal abrasive powder (wherein MA)+Is CH3NH3 +) The XRD diffraction pattern of (1) and the synchrotron radiation diffraction pattern of (2) and the XRD diffraction pattern after converting the synchrotron radiation light source signal into the standard XRD light source signal.
FIG. 3 is an atomic force microscope sectional view (FIG. 3.a) and a 3D model view (FIG. 3.b) of the single crystal thin film of the organic-inorganic composite perovskite material prepared in example 1, with different film thicknesses.
FIG. 4 is a graph showing the steady-state fluorescence emission spectrum and the ultraviolet-visible absorption spectrum of the single crystal thin film of the organic-inorganic composite perovskite material prepared in example 1.
FIG. 5 shows the organic-inorganic composite perovskite CH prepared in example 2 and example 33NH3PbI3(FIG. 5.a) and CH3NH3PbCl3(FIG. 5.b) Scanning Electron Microscopy (SEM) of a single crystal thin film of material.
Fig. 6 is an optical microscope image of the growth of the single crystal thin films of the organic-inorganic composite perovskite materials prepared in examples 4 to 6 on a high molecular Polymer (PET) substrate (fig. 6.a), a glass sheet (fig. 6.b), and a fluorine-doped tin dioxide conductive glass (FTO) sheet (fig. 6.c), respectively.
Detailed Description
As described above, the present invention provides a method for preparing a single crystal thin film of an organic-inorganic composite perovskite material, comprising the steps of:
(1) preparing a precursor solution of an organic-inorganic composite perovskite material, and treating a substrate to be used for growing a monocrystalline film;
(2) combining the substrates obtained by the treatment in the step (1) into a two-dimensional confinement structure, contacting the two-dimensional confinement structure with a precursor solution of the perovskite material, and forming a precursor solution film through capillary action;
(3) under certain conditions, the precursor grows into single crystal in situ to obtain the single crystal film of the organic-inorganic composite perovskite material.
In a preferred embodiment, the preparation method further comprises the following steps:
(4) and (4) removing the precursor solvent in the single crystal film of the organic-inorganic composite perovskite material prepared in the step (3) to obtain the final single crystal film of the organic-inorganic composite perovskite material.
In one embodiment of the present invention, in the step (1), the substrate for single crystal thin film growthThe processing method comprises the following steps: and sequentially placing the substrate in deionized water, absolute ethyl alcohol and acetone solution, respectively carrying out ultrasonic treatment for 15-30 min, drying by using nitrogen, and introducing oxygen for 0-20 min under the irradiation of ultraviolet light. Non-limiting, and possible reasons are that growing large-area single crystal thin films requires minimizing nucleation sites, the substrate surface is required to be very clean, contamination of the substrate surface can be removed by washing with deionized water, absolute ethanol, acetone, and UV-O3The further cleaning and hydrophilic treatment of the perovskite precursor solution can improve the wettability of the perovskite precursor solution, so that the perovskite precursor solution is uniformly spread on the surface of the substrate.
In one embodiment of the present invention, in step (2), the substrate can be combined into a two-dimensional domain-limiting structure in any way. The contact mode of the substrate and the precursor solution includes, but is not limited to, infiltrating the precursor solution into the two-dimensional confinement structure of the substrate combination in a dropwise manner to form a precursor solution film; or putting the substrate partially or completely into the precursor solution to form the precursor solution film. The perovskite precursor solution film on the substrate can be connected with a large amount of precursor solution in a contact mode, so that raw materials are consumed when the single crystal film continuously grows in the precursor solution film, and the raw materials are continuously supplemented into the liquid film from the solution through a small concentration difference, thereby being beneficial to growing the large-area perovskite single crystal film.
In one embodiment of the present invention, in the step (3), the growth temperature of the perovskite material single crystal thin film may be 0 to 200 ℃, preferably 50 to 150 ℃, and more preferably 80 to 110 ℃. Without limitation, the possible reasons are that the growth temperature and the solvent evaporation rate of the single crystal thin film are important single crystal growth regulating factors: when the temperature is too high, the shape of the single crystal thin film becomes irregular, and the crystallinity is reduced; the temperature is too low, the growth period of the single crystal is too long, the experimental efficiency is not good, and the generation of an amorphous phase can be caused by too low temperature; the evaporation rate is too high, a large amount of bulk phase single crystals can be generated competitively, raw materials are wasted, crystal defects are increased, and the crystal quality is reduced; the evaporation rate is too slow, and the growth period of the single crystal is too long, so that the experimental efficiency is not good.
In one embodiment of the present invention, the perovskite single crystal thin film in step (4) may be subjected to removal of the precursor solvent by means including, but not limited to, baking in a baking machine, baking in an oven, baking in a vacuum oven, and the like. Without limitation, a possible reason is that failure to remove the solvent sufficiently can result in the growth of a large number of small grains on the surface of the single crystal film, affecting the quality of the single crystal film.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with reference to the following embodiments and the accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Preparation of perovskite Single Crystal film
(1) Selecting PbBr2And CH3NH3Br is a precursor raw material of the perovskite type material, and the molar ratio of Br is 1:1 is dissolved in N, N-Dimethylformamide (DMF) to prepare a precursor solution of 0.7 mol/L; respectively carrying out ultrasonic treatment on the selected monocrystalline silicon wafer substrate in deionized water, absolute ethyl alcohol and acetone for 15min, and carrying out blow-drying on the monocrystalline silicon wafer substrate by using nitrogen gas to obtain UV-O3The treatment is carried out for 20 min.
(2) Combining two monocrystalline silicon wafer substrates together under the pressure of more than 1kPa, and then immersing one end of the monocrystalline silicon wafer into the prepared perovskite precursor solution.
(3) And (3) placing the substrate solution system containing the precursor solution film on a hot table at 100 ℃ and heating for 48h for in-situ growth to obtain the organic-inorganic composite perovskite material single crystal film.
(4) And transferring the substrate and the film into a vacuum oven, and drying for 48 hours at 100 ℃ to obtain the final organic-inorganic composite perovskite material single crystal film.
Example 1 preparation of the obtained organic-inorganic composite perovskite CH3NH3PbBr3A single crystal thin film of material.
FIG. 1 shows the organic-inorganic composite perovskite CH prepared in example 13NH3PbBr3Scanning Electron Microscopy (SEM) of a single crystal thin film of material. As can be seen from the figure, the perovskite single crystal thin film obtained by the process has high crystal quality, smooth and flat surface without defects, very sharp side face, high crystallization degree and large area, and the diameter and the length of the area of the thin film can reach 500 mu m. The defect-free single crystal film can greatly reduce the trap state density of the film, improve the carrier service life and the diffusion length of the film, and further improve the performance of a prepared device.
FIG. 2 shows MABr powder (wherein MA is measured under a standard XRD light source) of the organic-inorganic composite perovskite material single crystal thin film prepared in example 2+Is CH3NH3 +)，PbBr2Powder and MAPbBr3Single crystal abrasive powder (wherein MA)+Is CH3NH3 +) The XRD diffraction pattern of (1) and the synchrotron radiation diffraction pattern of (2) and the XRD diffraction pattern after converting the synchrotron radiation light source signal into the standard XRD light source signal. As can be seen, the two origins in the synchrotron radiation diffraction pattern represent the (100) and (300) crystallographic plane signals, respectively, of the single-crystal thin film. The figure shows only the signal of the (l00) crystal plane family, which proves that the single crystal film has excellent (l00) crystal plane orientation, and the figure does not contain any polycrystalline ring, which proves that the film is a perfect single crystal film. In the XRD diffraction pattern converted by the Bragg equation, corresponding diffraction at the 2 theta of 14.9 degrees and 45.9 degrees respectively represents the characteristic diffraction peaks of the (100) crystal face and the (300) crystal face of the perovskite crystal, and compared with the powder X-ray diffraction pattern of perovskite bulk phase single crystal prepared under the same solution condition and raw materials, the perovskite single crystal film prepared by the method has good crystallinity and crystal orientation.
FIG. 3 is an atomic force microscope cross-sectional view and a 3D model of the single crystal thin film of the organic-inorganic composite perovskite material prepared in example 1 with different film thicknesses. As can be seen from the figure, the perovskite single crystal thin film prepared by the embodiment can be obtained within the range of 10nm to 5 μm, the surface of the film is flat, smooth and free of defects, the film has high crystal quality, and the perovskite single crystal thin film can meet the requirements of various devices on different film thicknesses.
FIG. 4 is a graph showing the steady-state fluorescence emission spectrum and the ultraviolet-visible absorption spectrum of the single crystal thin film of the organic-inorganic composite perovskite material prepared in example 1. From the figure, it can be seen that the fluorescence emission peak is very sharp, no displacement exists relative to bulk phase single crystal, the light absorption section is very sharp, and no tail state exists, which indicates that the perovskite single crystal film prepared by the method has good crystallinity and high crystal quality.
The defect state density and the carrier mobility of the single crystal thin film of the organic-inorganic composite perovskite material prepared in the example 1 are respectively 4.8 multiplied by 1010cm-3And 15.7cm2V-1s-1And is equivalent to bulk single crystal, which shows that the crystal has good crystal quality.
Example 2
The preparation process differs from example 1 only in that: in step (1), PbI is used2And CH3NH3I is a precursor raw material of the perovskite material, and gamma-butyrolactone (GBL) is used as a precursor solvent to prepare a 1.2mol/L solution.
Example 2 preparation of the obtained organic-inorganic composite perovskite CH3NH3PbI3A single crystal thin film of material.
FIG. 5.a shows the organic-inorganic composite perovskite CH prepared in example 23NH3PbI3Scanning Electron Microscopy (SEM) of single crystal thin films of material. As can be seen from the figure, the perovskite single crystal thin film obtained by the process has high crystal quality, smooth and flat surface without defects, very sharp side face, high crystallization degree and large area, and the diameter and the length of the area of the thin film can reach 500 mu m. The defect-free single crystal film can greatly reduce the trap state density of the film, improve the carrier service life and the diffusion length of the film, and further improve the performance of a prepared device.
Example 3
The preparation process differs from example 1 only in that: in step (1), PbCl is used2And CH3NH3Cl is a precursor raw material of the perovskite material, and dimethyl sulfoxide (DMSO) is used as a precursor solvent to prepare 2.0mol/L solution.
Example 3 preparation of the obtained organic-inorganic composite perovskite CH3NH3PbCl3A single crystal thin film of material.
FIG. 5.b shows the organic-inorganic composite perovskite CH prepared in example 33NH3PbCl3Scanning Electron Microscopy (SEM) of single crystal thin films of material. As can be seen from the figure, the single crystal thin film of the perovskite material obtained by the process has high crystal quality, smooth and flat surface without defects, very sharp side face, high crystallization degree, large area and the diameter and the length of the area of the thin film can reach 500 mu m. The defect-free single crystal film can greatly reduce the trap state density of the film, improve the carrier service life and the diffusion length of the film, and further improve the performance of a prepared device.
Example 4
The preparation process differs from example 1 only in that: in step (1), a high molecular Polymer (PET) substrate is used as a single crystal thin film growth substrate for the perovskite material.
Example 4 preparation of the obtained organic-inorganic composite perovskite CH3NH3PbBr3A single crystal thin film of material.
FIG. 6.a is the organic-inorganic composite perovskite CH prepared in example 43NH3PbBr3Optical microscopy of single crystal thin films of material grown on high molecular Polymer (PET) substrates. As can be seen from the figure, the single crystal thin film of the perovskite material obtained by the process has high crystal quality, smooth and flat surface without defects, very sharp side face, high crystallization degree, large area and the diameter and the length of the area of the thin film can reach 500 mu m. The defect-free single crystal film can greatly reduce the trap state density of the film, improve the carrier service life and the diffusion length of the film, and further improve the performance of a prepared device.
Example 5
The preparation process differs from example 1 only in that: in step (1), a glass plate is used as a substrate for growing a single crystal thin film of a perovskite material.
Example 5 preparation of the obtained organic-inorganic composite perovskite CH3NH3PbBr3A single crystal thin film of material.
FIG. 6.b shows the organic-inorganic composite perovskite CH prepared in example 53NH3PbBr3Optical microscopy images of single crystal thin films of material grown on glass slides. As can be seen from the figure, the single crystal thin film of the perovskite material obtained by the process has high crystal quality, smooth and flat surface without defects, very sharp side face, high crystallization degree, large area and the diameter and the length of the area of the thin film can reach 500 mu m. The defect-free single crystal film can greatly reduce the trap state density of the film, improve the carrier service life and the diffusion length of the film, and further improve the performance of a prepared device.
Example 6
The preparation process differs from example 1 only in that: in the step (1), fluorine-doped tin dioxide conductive glass (FTO) is used as a single crystal thin film growth substrate of the perovskite material.
Example 6 preparation of the obtained organic-inorganic composite perovskite CH3NH3PbBr3A single crystal thin film of material.
FIG. 6.c shows the organic-inorganic composite perovskite CH prepared in example 63NH3PbBr3Optical microscopy images of single crystal thin films of material grown on fluorine doped tin dioxide conductive glass (FTO). As can be seen from the figure, the single crystal thin film of the perovskite material obtained by the process has high crystal quality, smooth and flat surface without defects, very sharp side face, high crystallization degree, large area and the diameter and the length of the area of the thin film can reach 500 mu m. The defect-free single crystal film can greatly reduce the trap state density of the film, improve the carrier service life and the diffusion length of the film, and further improve the performance of a prepared device.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (26)

1. A preparation method of a single crystal thin film of an organic-inorganic composite perovskite material is characterized by comprising the following steps:
(1) preparing a precursor solution of an organic-inorganic composite perovskite material, and treating a substrate to be used for growing a monocrystalline film;
(2) combining the substrates obtained by the treatment in the step (1) into a two-dimensional confinement structure, contacting the two-dimensional confinement structure with a precursor solution of the perovskite material, and forming a thin film of the precursor solution through capillary action;
(3) under certain conditions, the precursor grows into single crystal in situ to obtain the single crystal film of the organic-inorganic composite perovskite material.
2. The method of claim 1, further comprising the steps of:
(4) and (4) removing the precursor solvent in the single crystal film of the organic-inorganic composite perovskite material prepared in the step (3) to obtain the final single crystal film of the organic-inorganic composite perovskite material.
3. The production method according to claim 1, wherein in step (1), the precursor of the organic-inorganic composite perovskite material comprises at least one compound of formula AX and at least one compound of formula BX2Wherein A is selected from CH3NH3 +，CH3CH2NH3 +，NH2CH＝NH2 +，CH3(CH2)2NH3 +，CH3(CH2)3NH3 +And C6H5(CH2)2NH3 +One or a mixture thereof; b is selected from Pb2+，Sn2+And Ge2+One or a mixture thereof; x is selected from Cl-，Br-And I-Or a mixture thereof.
4. The process according to claim 3, wherein in the step (1), the compound of formula AX is reacted with the compound of formula BX2The molar ratio of the compound (1) to the compound (10) is 1:1 to 10.
5. The process of claim 4, wherein the compound of formula AX is reacted with a compound of formula BX2The molar ratio of the compound (1) to the compound (3) is 1:1 to 3.
6. The method according to claim 1, wherein in step (1), the solvent of the precursor solution is one or more selected from tetrahydrofuran, gamma-butyrolactone (GBL), acetonitrile, aniline, dimethyl sulfoxide (DMSO), and N, N-Dimethylformamide (DMF).
7. The method according to claim 6, wherein in the step (1), the solvent of the precursor solution is selected from one or more of gamma-butyrolactone (GBL), dimethyl sulfoxide (DMSO), and N, N-Dimethylformamide (DMF).
8. The preparation method according to claim 1, wherein in the step (1), the concentration of the precursor solution is 0.01-5 mol/L.
9. The preparation method according to claim 8, wherein in the step (1), the concentration of the precursor solution is 0.5-2.5 mol/L.
10. The method according to claim 1, wherein in the step (1), the substrate for growing the single crystal thin film is selected from the group consisting of a silicon wafer, a quartz wafer, a glass wafer, a high molecular Polymer (PET) substrate, and indium oxideTin conductive glass (ITO) sheet, fluorine-doped SnO2Conductive glass (FTO) sheet, graphene substrate, mica sheet.
11. The production method according to claim 1, wherein in the step (1), the substrate for single crystal thin film growth is treated by: and sequentially placing the substrate in deionized water, absolute ethyl alcohol and acetone solution, respectively carrying out ultrasonic treatment for 15-30 min, drying by using nitrogen, and introducing oxygen for 0-20 min under the irradiation of ultraviolet light.
12. The method according to claim 1, wherein in the step (2), the substrate is contacted with the precursor solution in a manner that comprises: the precursor solution is infiltrated into a two-dimensional confinement structure combined by the substrates in a dropwise adding mode to form a precursor solution film; or putting the substrate partially or completely into the precursor solution to form the precursor solution film.
13. The method according to claim 1, wherein the temperature of the in-situ growth in the step (3) is 0 to 200 ℃.
14. The method according to claim 13, wherein the temperature of the in-situ growth in the step (3) is 50 to 150 ℃.
15. The method according to claim 14, wherein the temperature of the in-situ growth in the step (3) is 80 to 110 ℃.
16. The method according to claim 1, wherein the in-situ growth time in step (3) is 6h to 5 d.
17. The method according to claim 16, wherein the in-situ growth time in step (3) is 24 to 48 hours.
18. The production method according to claim 1, wherein in the step (3), the thickness of the single crystal thin film is regulated by a pressure applied to the substrate.
19. The production method according to claim 18, wherein the thickness of the single crystal thin film decreases non-linearly with an increase in pressure applied to the substrate, and the single crystal thin film is formed when the pressure is more than 1 kPa; when the pressure is more than 200kPa, the thickness of the single crystal film can reach the nanometer level, the accurate measurement is difficult when the pressure is increased continuously, and the thickness of the single crystal film can reach 10nm after the pressure is increased to the maximum.
20. The production method according to claim 1, wherein in the step (3), the organic-inorganic composite perovskite material comprises at least one of the structural formula ABX3Wherein A is selected from CH3NH3 +，CH3CH2NH3 +，NH2CH＝NH2 +，CH3(CH2)2NH3 +，CH3(CH2)3NH3 +And C6H5(CH2)2NH3 +One or a mixture thereof; b is selected from Pb2+，Sn2+And Ge2+One or a mixture thereof; x is selected from Cl-，Br-And I-Or a mixture thereof.
21. The method according to claim 1, wherein in the step (4), the precursor solvent in the single crystal thin film is removed by one or more of baking in a hot stage, an oven or a dry box.
22. The production method according to claim 1, wherein in the step (4), the removal time of the precursor solvent is 12h to 5d depending on the perovskite component; the removal temperature of the precursor solvent is 50-150 ℃.
23. A single crystal thin film of an organic-inorganic composite perovskite material prepared by the method as claimed in any one of claims 1 to 22, wherein the thickness of the single crystal thin film is adjustable between micron and nanometer scale.
24. The single crystal thin film of an organic-inorganic composite perovskite material as claimed in claim 23, wherein the thickness of the single crystal thin film is adjustable in a range of 10nm to 10 μm, and the film thickness is uniform.
25. Use of a single crystal thin film of an organic-inorganic composite perovskite material prepared by the method of any one of claims 1 to 22 or as claimed in claim 23 or 24, characterized in that it is used in an optoelectronic device.
26. Use according to claim 25, in a solar cell.
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