CN108922972B - Perovskite thin film, perovskite solar cell and preparation method thereof - Google Patents

Perovskite thin film, perovskite solar cell and preparation method thereof Download PDF

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CN108922972B
CN108922972B CN201810685274.7A CN201810685274A CN108922972B CN 108922972 B CN108922972 B CN 108922972B CN 201810685274 A CN201810685274 A CN 201810685274A CN 108922972 B CN108922972 B CN 108922972B
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CN108922972A (en
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方俊锋
李晓冬
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention relates to a perovskite thin film, a perovskite solar cell and a preparation method thereof. The perovskite thin film comprises perovskite ABX3Organic-inorganic hybrid materials and polymers obtained by polymerizing acrylate monomers. The preparation method comprises the following steps: mixing acrylate monomer, AX and BX2Dissolving in a solvent to obtain a perovskite precursor solution; forming the perovskite precursor solution on a substrate; sequentially carrying out annealing treatment and illumination treatment on the substrate with the perovskite precursor solution to obtain a perovskite thin film; wherein the acrylate undergoes polymerization during the light treatment. The perovskite thin film protects the perovskite crystal boundary, and the stability of the perovskite thin film is good. The perovskite solar cell and the preparation method thereof are applied, so that the perovskite solar cell has high conversion efficiency and good stability.

Description

Perovskite thin film, perovskite solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite thin film, a perovskite solar cell and a preparation method thereof.
Background
Perovskite solar cells have high efficiency and low cost, and have attracted people's attention in recent years. At present, the biggest bottleneck restricting the perovskite solar cell to be practical is the stability thereof. Therefore, how to maximize the stability of the product while maintaining its high efficiency has become a significant research direction.
The stability of perovskite solar cells depends to some extent on the stability of the perovskite thin film. In the conventional perovskite thin film preparation method, the perovskite thin film prepared by the solution method generally contains a great number of surface and grain boundary defects, so that water, oxygen and the like in the air can permeate into the interior of the perovskite through the defects, and the decomposition of the perovskite is further caused. Meanwhile, since the interface defects are unstable in energy, they are easily attacked by external factors (such as light, electric field, heat, etc.), and the decomposition of perovskite is also accelerated. Therefore, in order to improve the stability of the perovskite thin film, it is necessary to protect the grain boundaries of the perovskite.
Disclosure of Invention
Therefore, the perovskite thin film and the preparation method thereof need to solve the problem of instability of the perovskite thin film, the perovskite thin film protects the perovskite grain boundary, and the stability of the perovskite thin film is good; the perovskite solar cell and the preparation method thereof are applied, so that the perovskite solar cell has high conversion efficiency and good stability.
A perovskite thin film comprising perovskite ABX3Organic-inorganic hybrid materials and polymers obtained by polymerizing acrylate monomers.
In the perovskite thin film, the polymer contains C ═ O functional groups and C ═ C functional groups, wherein the C ═ O functional groups can react with B ions (such as Pb) at perovskite grain boundaries2+、Sn2+、Ge2+Etc.) can effectively regulate the growth of the perovskite film through weak interaction of coordination bonds, so that the perovskite film is uniform and compact, has no obvious holes, and effectively passivates the crystal boundary defects of the perovskite film, thereby improving the stability of the perovskite film. With C ═ O functional groups and B ions (e.g. Pb)2+、Sn2+、Ge2+Etc.) can make the polymer effectively adhere to the crystal boundary, thereby forming a compact protective layer at the crystal boundary, further blocking the decomposition of water, oxygen and external factors on the perovskite and improving the stability of the perovskite battery. Therefore, the polymer can not only be used as a protective layer of perovskite grain boundaries, but also can passivate the grain boundariesThe stability of the perovskite thin film can be synergistically improved.
In one embodiment, the acrylate monomer is one or more of methyl methacrylate, ethyl methacrylate, and ethyl cyanoacrylate.
In one embodiment, the mass percentage of the polymer in the perovskite thin film is 0.3% to 2%.
In one embodiment, the perovskite ABX3In the organic-inorganic hybrid material, A is organic amine cation, and B is Pb2+、Sn2+、Ge2+X is a halogen anion or SCN-。
A method of preparing a perovskite thin film, the method comprising the steps of:
mixing acrylate monomer, AX and BX2Dissolving in a solvent to obtain a perovskite precursor solution;
forming the perovskite precursor solution on a substrate;
sequentially carrying out annealing treatment and illumination treatment on the substrate with the perovskite precursor solution to obtain a perovskite thin film; wherein the acrylate undergoes polymerization during the light treatment.
In the preparation method of the perovskite thin film, the acrylate monomer in the perovskite precursor solution can independently perform polymerization reaction under the action of illumination to obtain the polymer. The reaction steps are simple and easy to implement, other reaction conditions are not needed, and industrialization is easy to realize.
During the reaction, the acrylate contains C ═ O and C ═ C functional groups, where the C ═ O functional groups interact with the B ions at the perovskite grain boundaries (e.g., Pb)2+、Sn2+、Ge2+Etc.) to passivate grain boundary defects by weak interaction through coordination bonds. With C ═ O functional groups and B (e.g. Pb)2+、Sn2+、Ge2+Etc.) can be effectively attached to grain boundaries, and a C ═ C functional group in the acrylate undergoes a polymerization reaction by light irradiation treatment, thereby forming a dense protective layer at the grain boundaries to block water, oxygen and oxygenThe decomposition of the perovskite by external factors improves the stability of the perovskite film.
In one embodiment, A in said AX is an organic amine cation, X is a halide anion or SCN-(ii) a The BX2B in (A) is Pb2+、Sn2+、Ge2+Any one of them.
In one embodiment, the temperature of the annealing treatment is 80-100 ℃, and the time is 5-10 min.
In one embodiment, the light treatment is ultraviolet, infrared or sunlight irradiation for 5-30 min.
The perovskite solar cell comprises a hole transport layer, a perovskite thin film and an electron transport layer which are arranged in a laminated manner, wherein the perovskite thin film comprises perovskite ABX3Organic-inorganic hybrid materials and polymers obtained by polymerizing acrylate monomers.
The perovskite thin film is uniform and compact, has no obvious cavity, and has excellent stability. Therefore, the perovskite solar cell using the perovskite thin film not only has high conversion efficiency, but also has good stability.
A method of fabricating a perovskite solar cell, the method comprising the steps of:
providing a substrate;
forming a hole transport layer on the substrate; and
forming a perovskite thin film on the hole transport layer by adopting the preparation method; and
forming an electron transport layer on the perovskite thin film; and
and forming an electrode on the electron transport layer.
The preparation method of the perovskite solar cell has the advantages of simplicity and easiness in operation. The obtained perovskite solar cell has high conversion efficiency and good stability.
Drawings
FIG. 1 is an infrared spectrum of a perovskite thin film of example 1 of the present invention before and after light irradiation treatment, in which a is an infrared curve of the perovskite thin film after light irradiation treatment and b is an infrared curve of the perovskite thin film before light irradiation treatment;
FIG. 2 is a plan and sectional scanning electron microscope image of perovskite thin films prepared in example 1 and comparative example 1 of the present invention, in which b is a plan scanning electron microscope image of perovskite thin films prepared in example 1, d is a sectional scanning electron microscope image of perovskite thin films prepared in example 1, a is a plan scanning electron microscope image of perovskite thin films prepared in comparative example 1, and c is a sectional scanning electron microscope image of perovskite thin films prepared in comparative example 1;
FIG. 3 is a steady state fluorescence spectrum of the perovskite thin films prepared in example 1 of the present invention and comparative example 1, in which c is a fluorescence spectrum of the perovskite thin film of comparative example 1 and d is a fluorescence spectrum of the perovskite thin film of example 1;
FIG. 4 is a time-resolved fluorescence spectrum of perovskite thin films prepared according to example 1 and comparative example 1 of the present invention, in which e is the time-resolved fluorescence spectrum of the perovskite thin film of example 1 and f is the fluorescence spectrum of the perovskite thin film of comparative example 1;
FIG. 5 is a comparison of the X-ray diffraction (XRD) patterns of the perovskite thin films prepared according to the present invention in example 1 and comparative example 1, wherein h is the X-ray diffraction curve of the perovskite thin film of comparative example 1 and g is the X-ray diffraction curve of the perovskite thin film of example 1;
FIG. 6 is a schematic structural diagram of a perovskite solar cell of the present invention, in which 1 is a substrate, 2 is a hole transport layer, 3 is a perovskite thin film, 4 is an electron transport layer, and 5 is an electrode;
fig. 7 is a graph comparing the stability of the perovskite solar cells of example 7 of the present invention and comparative example 2, where i is the stability in air of the perovskite solar cell of example 7 and j is the stability in air of the perovskite solar cell of comparative example 2.
Detailed Description
The perovskite thin film, the perovskite solar cell and the preparation method thereof provided by the invention are further explained below.
The invention provides calcium titaniumThe mineral film comprises perovskite ABX3Organic-inorganic hybrid materials and polymers obtained by polymerizing acrylate monomers.
The mass percentage of the polymer in the perovskite thin film is 0.3% -2%. In the application of the perovskite thin film, such as in a perovskite solar cell, in view of the improvement effect of the polymer on the conversion efficiency and stability of the cell, it is preferable that the mass percentage of the polymer in the perovskite thin film is 0.3% to 1%.
The perovskite ABX3In the organic-inorganic hybrid material, A is organic amine cation, and B is Pb2+、Sn2+、Ge2+X is a halogen anion or SCN-. Preferably, A is CH3NH3 +、HC(NH2)2 +、CH3CH2NH3 +Wherein X is Cl-、Br-、I-Any one of them. Due to CH3NH3PbI3Has diffusion lengths of 130nm and 100nm, a forbidden bandwidth of 1.51eV, and good absorption in the range of 400nm to 800nm, respectively, and thus, the perovskite ABX3The organic-inorganic hybrid material is further preferably CH3NH3PbI3。
The acrylate monomer is one or more of methyl methacrylate, ethyl methacrylate and ethyl cyanoacrylate. Since the cyano group in the ethyl cyanoacrylate can also react with the B ion (e.g. Pb)2+、Sn2+、Ge2+Etc.) to generate weak interaction, which is more beneficial to passivating the crystal boundary defect and improving the stability of the perovskite film. Meanwhile, the ethyl cyanoacrylate can be polymerized under mild conditions (illumination or spontaneous polymerization in air), and the perovskite thin film is easily prepared by a low-temperature solution method. In addition, the ethyl cyanoacrylate is liquid at room temperature, is easier to be doped into the perovskite precursor solution, and the content of the ethyl cyanoacrylate in the perovskite thin film can be adjusted in a larger range. Therefore, the acrylic acid ester is more preferably methyl cyanoacrylate.
In the perovskite thin film, the polymer contains C ═ O functional groups and C ═ C functional groups, wherein the C ═ O functional groups can react with B ions (such as Pb) at perovskite grain boundaries2+、Sn2+、Ge2+Etc.) can effectively regulate the growth of the perovskite film through weak interaction of coordination bonds, so that the perovskite film is uniform and compact, has no obvious holes, and effectively passivates the crystal boundary defects of the perovskite film, thereby improving the stability of the perovskite film. With C ═ O functional groups and B ions (e.g. Pb)2+、Sn2+、Ge2+Etc.) can make the polymer effectively adhere to the crystal boundary, thereby forming a compact protective layer at the crystal boundary, further blocking the decomposition of water, oxygen and external factors on the perovskite and improving the stability of the perovskite battery. Therefore, the polymer can be used as a protective layer of perovskite grain boundaries, can passivate the defects of the grain boundaries, and can synergistically improve the stability of the perovskite thin film.
The invention also provides a preparation method of the perovskite thin film, which comprises the following steps:
s1, mixing acrylate monomer, AX and BX2Dissolving in a solvent to obtain a perovskite precursor solution;
s2, forming the perovskite precursor solution on a substrate;
s3, carrying out annealing treatment and illumination treatment on the substrate with the perovskite precursor solution in sequence to obtain a perovskite thin film; wherein the acrylate undergoes polymerization during the light treatment.
In step S1, the BX2The molar ratio of the compound to AX is 1 (0.8-1.2), preferably 1:1.
A in the AX is organic amine cation, X is halogen anion or SCN-. Preferably, A is CH3NH3 +、HC(NH2)2 +、CH3CH2NH3 +Wherein X is Cl-、Br-、I-Any one of them. Due to the perovskite ABX3Organic-inorganic hybridThe chemical substance is more preferably CH3NH3PbI3Therefore, the AX correspondence is preferably CH3NH3I。
The BX2B in (A) is Pb2+、Sn2+、Ge2+X is a halogen anion or SCN-. Preferably, B is Pb2+、Sn2+Wherein X is Cl-、Br-、I-Any one of them. Due to the perovskite ABX3The organic-inorganic hybrid material is further preferably CH3NH3PbI3Thus, the BX2The correspondence is preferably PbI2。
The solvent is a mixed solvent composed of N, N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide in the mixed solvent is (3-5): 1, preferably 4: 1.
In step S3, the temperature of the annealing treatment is 80-100 ℃ and the time is 5-10 min. And forming a perovskite precursor solution on the substrate, and then carrying out annealing treatment to crystallize the perovskite precursor solution to obtain the perovskite thin film. In view of the requirement for sufficiently complete crystallization, a temperature of 100 ℃ is preferred, and a time of 10min is preferred.
The illumination treatment is ultraviolet, infrared or sunlight irradiation for 5-30 min. And further carrying out illumination treatment on the perovskite thin film formed by crystallization after annealing treatment to enable the acrylate in the perovskite thin film to be subjected to in-situ polymerization to generate a stable polymer. In view of the ready availability of sunlight and the need for complete polymerization of the acrylate, it is preferred that the illumination is sunlight for a period of 10 min.
The acrylate is one or more of methyl methacrylate, ethyl methacrylate and ethyl cyanoacrylate, and preferably ethyl cyanoacrylate. The in situ reaction equation for ethyl cyanoacrylate is shown below:
Figure BDA0001711521110000071
in the preparation method of the perovskite thin film, the acrylate monomer in the perovskite precursor solution can independently perform polymerization reaction under the action of illumination to obtain the polymer. The reaction steps are simple and easy to implement, other reaction conditions are not needed, and industrialization is easy to realize.
During the reaction, the acrylate contains C ═ O and C ═ C functional groups, where the C ═ O functional groups interact with the B ions at the perovskite grain boundaries (e.g., Pb)2+、Sn2+、Ge2+Etc.) to passivate grain boundary defects by weak interaction through coordination bonds. With C ═ O functional groups and B (e.g. Pb)2+、Sn2+、Ge2+Etc.) can make the polymer effectively adhere to the crystal boundary, and after the light treatment, the C ═ C functional group in the acrylate has polymerization reaction, thereby forming a compact protective layer at the crystal boundary, blocking the decomposition action of water, oxygen and external factors on the perovskite, and improving the stability of the perovskite thin film.
The invention also provides a perovskite solar cell which comprises a hole transport layer 2, a perovskite thin film 3 and an electron transport layer 4 which are arranged in a laminated manner, wherein the perovskite thin film 3 comprises perovskite ABX3Organic-inorganic hybrid materials and polymers obtained by polymerizing acrylate monomers.
The perovskite battery further comprises a substrate 1 and an electrode 5.
Specifically, as shown in fig. 4, the perovskite solar cell includes a substrate 1, a hole transport layer 2, a perovskite thin film 3, an electron transport layer 4, and an electrode 5, which are sequentially stacked.
The material of the substrate 1 is not limited, and can be any one of a silicon wafer, glass and a stainless steel sheet. Since ITO is a metal compound having a good transparent conductive property, and has characteristics of a forbidden bandwidth, high light transmittance in a visible spectrum region, low resistivity, and the like, the substrate 1 is preferably ITO conductive glass.
The hole transport layer 2 is poly [3- (methylamine butyrate) thiophene](PSCT-N) material layer with thickness of 5-20 nm, and P3CT-N energy level of 5 relative to conventional hole transport layer PEDOT: PSS (energy level of 5.11 eV).26eV, with selected perovskite CH3NH3PbI3The valence band (5.3eV) is closer, and the reduction of the cell efficiency caused by the energy level mismatching can be effectively avoided. P3CT-N is preferably 10nm thick. The chemical structural formula of the P3CT-N is as follows:
Figure BDA0001711521110000081
the thickness of the perovskite thin film 3 is 400 nm-500 nm. In view of the balanced transport of carriers, a thickness of 450nm is preferable.
The electron transport layer 4 comprises a PCBM layer, a C60 layer and a BCP layer which are sequentially stacked, wherein the thickness of the PCBM layer is 20 nm-50 nm, the thickness of the C60 layer is 20 nm-40 nm, the thickness of the BCP layer is 8 nm-10 nm, and the thickness of the electron transport layer 4 is 50 nm-100 nm. PCBM is prepared by spin coating with a solution method, can effectively penetrate into and cover cavities possibly existing on the surface of perovskite, and the preferred thickness is 20 nm; the C60 is prepared by vacuum evaporation, so that the obtained C60 layer is more compact and uniform, and the preferred thickness is 40 nm; and BCP is used as a hole blocking layer to inhibit recombination at an electrode interface and improve the performance of the device, and the preferred thickness is 8 nm.
The thickness of the electrode 5 is 100nm to 300nm, and the material of the electrode 5 is not limited, but the electrode 5 is preferably a copper electrode in consideration of the high cost of gold as an electrode and the short service life of silver as an electrode.
The perovskite thin film is uniform and compact, has no obvious cavity, and has excellent stability. Therefore, the perovskite solar cell using the perovskite thin film not only has high conversion efficiency, but also has good stability.
The invention also provides a preparation method of the perovskite solar cell. The preparation method comprises the following steps:
providing a substrate 1;
forming a hole transport layer 2 on the substrate 1; and
forming a perovskite thin film 3 on the hole transport layer 2 by adopting the preparation method of the perovskite thin film; and
forming an electron transport layer 4 on the perovskite thin film 3; and
an electrode 5 is formed on the electron transport layer 4.
The substrate 1 is made of ITO conductive glass, the ITO conductive glass is washed by an ITO cleaning agent and deionized water to remove grease and organic matters, then the ITO conductive glass is sequentially washed by deionized water, acetone and isopropanol in an ultrasonic mode, dried by nitrogen, and further processed by oxygen plasma.
The hole transport layer 2 is a P3CT-N material layer, the P3CT-N material layer is formed by spin coating of a P3CT-N solution, the rotating speed is 3000-4000 r/min, and the time is 45-60 seconds. The P3CT-N solution is a methanol solution of P3CT-N, and the concentration of the P3CT-N is 1 mg/mL-5 mg/mL.
The electron transport layer 4 comprises a PCBM layer, a C60 layer and a BCP layer which are sequentially stacked. The PCBM layer is formed by spin coating of PCBM solution, the rotating speed is 1500-2500 rpm, and the time is 50-80 seconds. The PCBM solution is a chlorobenzene solution of PCBM, and the concentration of the PCBM is 10 mg/mL-25 mg/mL. The C60 layer and the BCP layer are formed by a vacuum thermal evaporation method.
The electrode 5 is a copper electrode and is formed by a vacuum thermal evaporation method.
The preparation method of the perovskite solar cell has the advantages of simplicity and easiness in operation. The obtained perovskite solar cell has high conversion efficiency and good stability.
Hereinafter, the perovskite thin film, the perovskite solar cell and the preparation method thereof will be further described by the following specific examples.
Example 1:
mixing PbI with a molar ratio of 1:12(668.5mg) and CH3NH3I (230.5mg) and 5mg of ethyl cyanoacrylate were dissolved in 1mL of a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1 to obtain a perovskite precursor solution. Wherein, PbI2And CH3NH3The concentration of I is 1.45mmol/mL, and the cyanopropeneThe concentration of ethyl acetate was 5 mg/mL.
And spin-coating the perovskite precursor solution on an ITO glass substrate by a spin coater at the rotating speed of 4800 r/min for 20 s.
Then annealing for 10 minutes at 100 ℃ to form the perovskite thin film. After the perovskite thin film is formed, the perovskite thin film is polymerized through solar light treatment, and the light time is 10 minutes.
The resulting perovskite thin film comprises CH3NH3PbI3And a polymer of ethyl cyanoacrylate, wherein the mass percentage of the polymer of ethyl cyanoacrylate is 0.5%.
The infrared spectra of the perovskite thin film before and after the light treatment are shown in FIG. 1. As can be seen from fig. 1, ethyl cyanoacrylate was indeed present in the perovskite thin film before the light irradiation treatment. After the light irradiation treatment, the peak of the carbon-carbon double bond in the perovskite film disappears, which indicates that the ethyl cyanoacrylate is completely polymerized to form a polymer.
Example 2:
mixing PbI with a molar ratio of 1:12(668.5mg) and CH3NH3I (230.5mg) and 3mg of ethyl cyanoacrylate were dissolved in 1mL of a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide at a volume ratio of 4:1 to obtain a perovskite precursor solution. Wherein, PbI2And CH3NH3The concentration of I was 1.45mmol/mL, and the concentration of ethyl cyanoacrylate was 3 mg/mL.
And spin-coating the perovskite precursor solution on an ITO glass substrate by a spin coater at the rotating speed of 4800 r/min for 20 s.
Then annealing at 100 ℃ for 5 minutes to form the perovskite thin film. After the perovskite thin film is formed, the ethyl cyanoacrylate in the perovskite thin film is polymerized through solar light treatment, and the light irradiation time is 30 minutes.
The resulting perovskite thin film comprises CH3NH3PbI3And a polymer of ethyl cyanoacrylate, wherein the mass percentage of the polymer of ethyl cyanoacrylate is 0.3%.
Example 3:
will molePbI in the ratio of 1:0.82(668.5mg) and CH3NH3I (184.4mg) and 10mg of ethyl cyanoacrylate were dissolved in 1mL of a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 3:1 to obtain a perovskite precursor solution. Wherein, PbI2And CH3NH3The concentration of I was 1.45mmol/mL, and the concentration of ethyl cyanoacrylate was 10 mg/mL.
And spin-coating the perovskite precursor solution on an ITO glass substrate by a spin coater at the rotating speed of 4800 r/min for 20 s.
Annealing at 80 deg.c for 8 min to form perovskite film. After the perovskite film is formed, the ethyl cyanoacrylate in the perovskite film is polymerized by ultraviolet lamp irradiation treatment, and the irradiation time is 5 minutes.
The resulting perovskite thin film comprises CH3NH3PbI3And a polymer of ethyl cyanoacrylate, wherein the mass percentage of the polymer of ethyl cyanoacrylate is 1%.
Example 4:
mixing PbI with a molar ratio of 1:1.22(668.5mg) and CH3NH3I (276.6mg) and 20mg of ethyl cyanoacrylate were dissolved in 1mL of a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide at a volume ratio of 5:1 to obtain a perovskite precursor solution. Wherein, PbI2And CH3NH3The concentration of I was 1.45mmol/mL, and the concentration of ethyl cyanoacrylate was 20 mg/mL.
And spin-coating the perovskite precursor solution on an ITO glass substrate by using a spin coater at the rotating speed of 4800 r/min for 20 seconds.
And annealing at 90 deg.C for 10min to form perovskite film. After the perovskite film is formed, polymerizing ethyl cyanoacrylate in the perovskite film by irradiation treatment of an infrared lamp, wherein the irradiation time is 20 minutes.
The resulting perovskite thin film comprises CH3NH3PbI3And a polymer of ethyl cyanoacrylate, wherein the mass percentage of the polymer of ethyl cyanoacrylate is 2%.
Example 5:
PbI in a molar ratio of 1:12(668.5mg) and CH3NH3I (230.5mg) and 5mg of methyl methacrylate were dissolved in 1mL of a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide at a volume ratio of 4:1 to obtain a perovskite precursor solution. Wherein, PbI2And CH3NH3The concentration of I was 1.45mmol/mL, and the concentration of methyl methacrylate was 5 mg/mL.
And spin-coating the perovskite precursor solution on an ITO glass substrate by a spin coater at the rotating speed of 4800 r/min for 20 s.
Annealing at 80 deg.C for 5min to form perovskite film. After the perovskite film is formed, the methyl methacrylate in the perovskite film is polymerized by ultraviolet lamp illumination, and the illumination time is 20 minutes.
The resulting perovskite thin film comprises CH3NH3PbI3And a polymer of methyl methacrylate, wherein the mass percentage of the polymer of methyl methacrylate is 0.5%.
Example 6
Mixing PbI with a molar ratio of 1:12(668.5mg) and CH3NH3I (230.5mg) and 5mg of ethyl methacrylate were dissolved in 1mL of a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide at a volume ratio of 4:1 to obtain a perovskite precursor solution. Wherein, PbI2And CH3NH3The concentration of I was 1.45mmol/mL, and the concentration of ethyl methacrylate was 5 mg/mL.
And spin-coating the perovskite precursor solution on an ITO glass substrate by a spin coater at the rotating speed of 4800 r/min for 20 s.
Annealing at 80 deg.c for 5min to form perovskite film. After the perovskite film is formed, the ethyl methacrylate in the perovskite film is polymerized by ultraviolet lamp illumination, and the illumination time is 20 minutes.
The resulting perovskite thin film comprises CH3NH3PbI3And a polymer of ethyl methacrylate, wherein the mass percentage of the polymer of ethyl methacrylate is 0.5%.
Example 7:
as shown in fig. 6, the perovskite solar cell comprises a substrate 1, a hole transport layer 2, a perovskite thin film 3, an electron transport layer 4 and an electrode 5 which are sequentially stacked, and the preparation method is as follows:
the ITO conductive glass is used as a substrate 1, washed by an ITO cleaning agent and deionized water to remove grease and organic matters, then sequentially washed by deionized water, acetone and isopropanol by ultrasonic, dried by nitrogen and further treated by oxygen plasma.
And manufacturing the hole transport layer 2 on the processed ITO conductive glass by adopting a spin coating method. The hole transport layer 2 is a P3CT-N material layer and is formed by spin coating of a 2mg/mL methanol solution of P3CT-N, the rotation speed of a spin coater is 3500 rpm, the time is 45 seconds, and the thickness is 10 nm.
A perovskite thin film 3 was formed on the hole transport layer 2 by the preparation method of example 1 to have a thickness of 450 nm.
An electron transport layer 4 is manufactured on the perovskite thin film 3, a PCBM layer is formed by spin coating of 10mg/mL PCBM chlorobenzene solution, the rotating speed of a spin coater is 2000 rpm, the time is 60 seconds, and the thickness is 20 nm. Then, a C60 layer with a thickness of 40nm was formed on the PCBM layer by vacuum thermal evaporation, and a BCP layer with a thickness of 8nm was formed on the C60 layer by vacuum thermal evaporation.
A layer of copper is evaporated on the electron transport layer 4 by a vacuum thermal evaporation method to be used as an electrode 5, and the thickness is 300 nm.
Example 8:
as shown in fig. 6, the perovskite solar cell comprises a substrate 1, a hole transport layer 2, a perovskite thin film 3, an electron transport layer 4 and an electrode 5 which are sequentially stacked, and the preparation method is as follows:
the ITO conductive glass is used as a substrate 1, washed by an ITO cleaning agent and deionized water to remove grease and organic matters, then sequentially washed by deionized water, acetone and isopropanol by ultrasonic, dried by nitrogen and further treated by oxygen plasma.
And manufacturing the hole transport layer 2 on the processed ITO conductive glass by adopting a spin coating method. The hole transport layer 2 is a P3CT-N material layer and is formed by spin coating of a 1mg/mL methanol solution of P3CT-N, the rotation speed of a spin coater is 3000 r/min, the time is 45 seconds, and the thickness is 5 nm.
A perovskite thin film 3 was formed on the hole transport layer 2 by the preparation method of example 1 to have a thickness of 400 nm.
An electron transport layer 4 is manufactured on the perovskite thin film 3, a PCBM layer is formed by spin coating of PCBM chlorobenzene solution with the concentration of 15mg/mL, the rotating speed of a spin coater is 1500 revolutions per minute, the time is 80 seconds, and the thickness is 30 nm. Then, a C60 layer with a thickness of 20nm was formed on the PCBM layer by vacuum thermal evaporation, and a BCP layer with a thickness of 10nm was formed on the C60 layer by vacuum thermal evaporation.
A layer of copper is evaporated on the electron transport layer 4 by a vacuum thermal evaporation method to be used as an electrode 5, and the thickness is 100 nm.
Example 9:
as shown in fig. 6, the perovskite solar cell comprises a substrate 1, a hole transport layer 2, a perovskite thin film 3, an electron transport layer 4 and an electrode 5 which are sequentially stacked, and the preparation method is as follows:
the ITO conductive glass is used as a substrate 1, washed by an ITO cleaning agent and deionized water to remove grease and organic matters, then sequentially washed by deionized water, acetone and isopropanol by ultrasonic, dried by nitrogen and further treated by oxygen plasma.
And manufacturing the hole transport layer 2 on the processed ITO conductive glass by adopting a spin coating method. The hole transport layer 2 is a P3CT-N material layer and is formed by spin coating of a 3mg/mL methanol solution of P3CT-N, the rotation speed of a spin coater is 3600 r/min, the time is 60 seconds, and the thickness is 15 nm.
The perovskite thin film 3 was formed on the hole transport layer 2 by the preparation method of example 1 to have a thickness of 460 nm.
An electron transport layer 4 is manufactured on the perovskite thin film 3, a PCBM layer is formed by spin coating of a chlorobenzene solution of PCBM with the concentration of 18mg/mL, the rotating speed of a spin coater is 1800 rpm, the time is 70 seconds, and the thickness is 40 nm. Then, a layer of C60 with a thickness of 30nm was formed on the PCBM layer by vacuum thermal evaporation, and a layer of BCP with a thickness of 9nm was formed on the layer of C60 by vacuum thermal evaporation.
A layer of copper is evaporated on the electron transport layer 4 by a vacuum thermal evaporation method to be used as an electrode 5, and the thickness is 200 nm.
Example 10:
as shown in fig. 6, the perovskite solar cell comprises a substrate 1, a hole transport layer 2, a perovskite thin film 3, an electron transport layer 4 and an electrode 5 which are sequentially stacked, and the preparation method is as follows:
the ITO conductive glass is used as a substrate 1, washed by an ITO cleaning agent and deionized water to remove grease and organic matters, then sequentially washed by deionized water, acetone and isopropanol by ultrasonic, dried by nitrogen and further treated by oxygen plasma.
And manufacturing the hole transport layer 2 on the processed ITO conductive glass by adopting a spin coating method. The hole transport layer 2 is a P3CT-N material layer and is formed by spin coating of a 5mg/mL methanol solution of P3CT-N, the rotation speed of a spin coater is 4000 revolutions per minute, the time is 60 seconds, and the thickness is 20 nm.
A perovskite thin film 3 was formed on the hole transport layer 2 by the preparation method of example 1 to have a thickness of 500 nm.
An electron transport layer 4 is manufactured on the perovskite thin film 3, a PCBM layer is formed by spin coating of PCBM chlorobenzene solution with the concentration of 25mg/mL, the rotating speed of a spin coater is 2500 rpm, the time is 80 seconds, and the thickness is 50 nm. Then, a C60 layer with a thickness of 40nm was formed on the PCBM layer by vacuum thermal evaporation, and a BCP layer with a thickness of 10nm was formed on the C60 layer by vacuum thermal evaporation.
A layer of copper is evaporated on the electron transport layer 4 by a vacuum thermal evaporation method to be used as an electrode 5, and the thickness is 150 nm.
Comparative example 1:
comparative example 1 was the same as example 1 except that the perovskite precursor solution of comparative example 1 did not contain ethyl cyanoacrylate, and the resulting perovskite thin film did not contain a polymer of ethyl cyanoacrylate.
FIG. 2 is a scanning electron micrograph of the perovskite thin films of example 1 and comparative example 1 of the present invention, and it can be seen from FIG. 2 that the addition of ethyl cyanoacrylate can effectively induce uniform growth of perovskite to form a dense and uniform perovskite thin film. The perovskite thin film obtained in the embodiment 1 has uniform crystal size, is compact and uniform, and has no obvious holes or cracks; the perovskite thin film obtained in the comparative example 1 has different crystal sizes and obvious holes.
FIG. 3 is a graph showing the steady state fluorescence spectra of perovskite thin films according to example 1 of the present invention and comparative example 1. As can be seen from fig. 3, the addition of ethyl cyanoacrylate can blue-shift the fluorescence spectrum of the perovskite thin film, indicating that defects inside the perovskite are effectively suppressed.
FIG. 4 is a time-resolved fluorescence spectrum of the perovskite thin films of example 1 of the present invention and comparative example 1. The time-resolved fluorescence spectrum shows that the addition of ethyl cyanoacrylate can effectively prolong the service life of carriers in the perovskite thin film, and further the perovskite thin film can improve the efficiency of the battery when being applied to the perovskite solar battery.
FIG. 5 is a graph comparing the X-ray diffraction (XRD) patterns of the perovskite thin films of example 1 of the present invention and comparative example 1. As can be seen from fig. 5, the diffraction peak of the perovskite thin film containing ethyl cyanoacrylate did not show any shift, indicating that: the addition of ethyl cyanoacrylate does not enter the interior of the crystal structure of the perovskite, but exists only in the vicinity of the grain boundaries between the crystals.
Comparative example 2:
comparative example 2 was the same as example 7 except that the perovskite thin film obtained in comparative example 1 was used for the perovskite thin film of comparative example 2, and the perovskite thin film contained no polymer of ethyl cyanoacrylate.
The perovskite solar cell device efficiency vs. ratio of example 7 and comparative example 2 is shown in table 1.
TABLE 1
Figure BDA0001711521110000181
Fig. 7 is a graph comparing the stability in air of the perovskite solar cells of example 7 of the present invention and comparative example 2, with the humidity of air being: 40 to 60 percent. As can be seen from fig. 7, the stability of the perovskite solar cell of the present invention is significantly improved.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A preparation method of a perovskite thin film is characterized by comprising the following steps:
mixing acrylate monomer, AX and BX2Dissolving in a solvent to obtain a perovskite precursor solution;
forming the perovskite precursor solution on a substrate;
sequentially carrying out annealing treatment and illumination treatment on the substrate with the perovskite precursor solution to obtain a perovskite thin film; the acrylate monomer is subjected to polymerization reaction in the illumination treatment process to generate a polymer, and the mass percentage of the polymer in the perovskite thin film is 0.3% -2%.
2. The method for producing a perovskite thin film as claimed in claim 1, wherein A in AX is an organic amine cation, and X is a halogen anion or SCN-(ii) a The BX2B in (A) is Pb2+、Sn2+、Ge2+Any one of them.
3. The method for preparing a perovskite thin film according to claim 1, wherein the acrylate monomer is one or more of methyl methacrylate, ethyl methacrylate and ethyl cyanoacrylate.
4. The method for preparing the perovskite thin film as claimed in claim 1, wherein the annealing temperature is 80 ℃ to 100 ℃ and the annealing time is 5min to 10 min.
5. The method for preparing a perovskite thin film according to claim 1, wherein the light irradiation is ultraviolet, infrared or solar light irradiation for 5-30 min.
6. A perovskite thin film obtained by the method for producing a perovskite thin film according to any one of claims 1 to 5, wherein the perovskite thin film comprises a perovskite ABX3Organic-inorganic hybrid materials and polymers obtained by polymerizing acrylate monomers.
7. A perovskite solar cell comprising a hole transport layer, the perovskite thin film as claimed in claim 6 and an electron transport layer which are disposed in a stack.
8. A method of fabricating a perovskite solar cell, the method comprising the steps of:
providing a substrate;
forming a hole transport layer on the substrate; and
forming a perovskite thin film on the hole transport layer by the preparation method according to any one of claims 1 to 5; and
forming an electron transport layer on the perovskite thin film; and
and forming an electrode on the electron transport layer.
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CN110690355B (en) * 2019-09-26 2020-12-04 深圳市华星光电半导体显示技术有限公司 Perovskite thin film, preparation method thereof and photoelectric device
CN111106245A (en) * 2019-12-03 2020-05-05 华东师范大学 Perovskite battery for inhibiting electrode corrosion and preparation method thereof
CN113130823A (en) * 2019-12-30 2021-07-16 Tcl集团股份有限公司 Photoelectric device and preparation method thereof
CN111584717B (en) * 2020-05-15 2022-05-10 浙江大学 Method for improving efficiency of hybrid perovskite solar cell by aid of photo-thermal combined external field
CN111584716B (en) * 2020-05-15 2022-05-10 浙江大学 Method for repairing two-dimensional hybrid perovskite solar cell by thermal activation assisted light
CN114855283B (en) * 2021-01-20 2023-06-09 中国科学院福建物质结构研究所 Pb-based coordination polymer crystal and preparation method and application thereof
CN113637126A (en) * 2021-08-03 2021-11-12 西北工业大学 Star-polymer-doped perovskite solar cell and preparation method thereof
CN113512149B (en) * 2021-08-05 2023-08-01 重庆工商大学 Preparation method of flocculant based on visible light polymerization and using cesium triiodo-plumbate as initiator
CN113782678B (en) * 2021-08-17 2023-06-27 华东师范大学 Perovskite solar cell and preparation method thereof
CN114256422B (en) * 2021-12-07 2023-02-21 华能新能源股份有限公司 Perovskite solar cell for slowing down ion migration and preparation method thereof
CN114316948B (en) * 2022-01-06 2023-05-16 西北工业大学 Method for preparing flexible luminous gel by acrylic acid induced perovskite crystallization

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106170877A (en) * 2014-02-26 2016-11-30 联邦科学和工业研究组织 The method forming the photosensitive layer of perovskite light-sensitive unit
CN106634962A (en) * 2016-12-21 2017-05-10 电子科技大学 Preparation method of polymer modified perovskite particle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106170877A (en) * 2014-02-26 2016-11-30 联邦科学和工业研究组织 The method forming the photosensitive layer of perovskite light-sensitive unit
CN106634962A (en) * 2016-12-21 2017-05-10 电子科技大学 Preparation method of polymer modified perovskite particle

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Highly Stable and Luminescent Perovskite-Polymer Composites from a Convenient and Universal Strategy";Xin Y, Zhao H, Zhang J.;《ACS Applied Materials & Interfaces》;20180115;第10卷(第5期);第4977页实验部分以及附图1 *
"Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%";D Bi, Yi C, Luo J, et al.;《Nature Energy》;20160919;第1卷(第10期);第1页右栏最后一段、第4页实验部分以及附图1 *
D Bi, Yi C, Luo J, et al.."Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%".《Nature Energy》.2016,第1卷(第10期), *
Xin Y, Zhao H, Zhang J.."Highly Stable and Luminescent Perovskite-Polymer Composites from a Convenient and Universal Strategy".《ACS Applied Materials & Interfaces》.2018,第10卷(第5期), *

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