CN114824105B - Perovskite solar cell and preparation method thereof - Google Patents

Perovskite solar cell and preparation method thereof Download PDF

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CN114824105B
CN114824105B CN202210490739.XA CN202210490739A CN114824105B CN 114824105 B CN114824105 B CN 114824105B CN 202210490739 A CN202210490739 A CN 202210490739A CN 114824105 B CN114824105 B CN 114824105B
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perovskite
maac
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lead iodide
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CN114824105A (en
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胡汉林
梁潇
朱泉峣
周先放
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Shenzhen Polytechnic
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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
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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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Abstract

The invention discloses a perovskite solar cell and a preparation method thereof, wherein the preparation method comprises the following steps: providing a conductive substrate; preparing an electron transport layer on the conductive substrate; preparing a perovskite layer on the surface of the electron transport layer, wherein the perovskite layer comprises a perovskite body and MAAc; preparing a hole transport layer on the surface of the perovskite layer; and preparing an electrode on the surface of the hole transport layer. According to the invention, trace ionic liquid MAAc is added into the perovskite layer, and the MAAc can passivate and fill internal and surface defects of the perovskite layer, so that non-radiative recombination of photogenerated carriers is reduced, and the photoelectric conversion efficiency of the device is effectively improved.

Description

Perovskite solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of solar photovoltaics, in particular to a perovskite solar cell and a preparation method thereof.
Background
Organic-inorganic hybrid perovskite solar cells show great potential for development due to their unique properties including excellent power conversion efficiency, optimal band gap, high charge carrier mobility, low cost, long carrier lifetime, and large-scale processability. The photoelectric conversion of solar cells using perovskite as absorber reached 25.7%, which is comparable to commercial polysilicon solar cells. For the core components of perovskite devices, the quality of the perovskite absorber layer plays a critical role in device performance. Generally, perovskite thin films are prepared by evaporating a solvent from a precursor solution through a spin coating process, and defects are easily generated at grain boundaries and surfaces during crystallization. These defects can promote perovskite degradation and non-radiative recombination of photogenerated carriers, which can severely limit the efficiency and low fill factor of the device.
Accordingly, there is a need for improvement and development in the art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a perovskite solar cell and a preparation method thereof, which aims to solve the problems that the existing perovskite thin film has defects, resulting in non-radiative recombination of photo-generated carriers, and severely limiting the efficiency of devices.
The technical scheme of the invention is as follows:
the first aspect of the invention provides a method for preparing a perovskite solar cell, comprising the steps of:
providing a conductive substrate;
preparing an electron transport layer on the conductive substrate;
preparing a perovskite layer on the surface of the electron transport layer, wherein the perovskite layer comprises a perovskite body and methylamine acetic acid (MAAc);
preparing a hole transport layer on the surface of the perovskite layer;
and preparing an electrode on the surface of the hole transport layer.
According to the invention, the perovskite layer is modified by using the ionic liquid MAAc, so that the defects of the perovskite layer are effectively reduced, the non-radiative recombination of photogenerated carriers is reduced, and the photoelectric conversion efficiency of the device is effectively improved.
Optionally, in the perovskite layer, the mass ratio of the MAAc is 0.05-1%.
Optionally, the perovskite body is ABX 3 Wherein a comprises a methylamine cation, a formamidine cation, and a cesium cation, or a comprises a methylamine cation, a formamidine cation, and a potassium cation; b comprises lead cations; x includes chloride, bromide and iodide anions.
Optionally, the step of preparing a perovskite layer on the surface of the electron transport layer specifically comprises:
providing a mixed solution of lead iodide and MAAc, and providing an organic halide solution;
spin-coating the mixed solution of lead iodide and MAAc on the surface of the electron transport layer, and performing a first annealing treatment to obtain a lead iodide layer;
and spin-coating the organic halide solution on the surface of the lead iodide layer, and carrying out second annealing treatment to obtain the perovskite layer.
The method introduces trace ionic liquid MAAc into the lead iodide solution, and adopts a two-step spin coating technology to prepare the perovskite layer. The perovskite layer is prepared by a two-step spin coating method, anti-solvents such as chlorobenzene and the like are removed, the cost is effectively reduced, and the method has the characteristic of being more environment-friendly, and can realize rapid large-area device production. The spin coating process is mature in process technology, simple in preparation process and high in repetition rate.
Optionally, the preparation method of the mixed solution of lead iodide and MAAc comprises the following steps:
dissolving lead iodide in a solvent to obtain a lead iodide solution;
adding MAAc into the lead iodide solution to obtain a mixed solution of lead iodide and MAAc;
wherein the solvent is one or more than two of N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
Optionally, the mixed solution of lead iodide and MAAc consists of lead iodide, MAAc and solvent, wherein the addition amounts of the lead iodide, the MAAc and the solvent are respectively 0.5-3 mol, 0.5-50 mu L and 950-999.5 mL.
Optionally, in the step of spin-coating the mixed solution of lead iodide and MAAc on the surface of the electron transport layer, the spin-coating parameters include: the rotating speed is 1000-4000r/s, and the time is 20-60s;
and/or, the parameters of the first annealing treatment comprise: the temperature is 40-90 ℃ and the time is 10-120s.
Alternatively, the organic halide solution is a FAI, MACl, MABr and CsI containing solution; alternatively, the organic halide solution is a FAI, MACl, MABr and KI containing solution.
Optionally, the mass ratio of FAI, MACl, MABr, csI is 60 (6-10): (6-10): (1-2); or the mass ratio of FAI, MACl, MABr, KI is 60 (6-10): 1-2.
Optionally, in the step of spin-coating the organic halide solution on the surface of the lead iodide layer, the spin-coating parameters include: the rotating speed is 1000-4000r/s, and the time is 20-60s;
and/or, the parameters of the second annealing treatment comprise: the temperature is 90-130 ℃ and the time is 10-80min.
The second aspect of the invention provides a perovskite solar cell, wherein the perovskite solar cell is prepared by the method of the invention.
Drawings
FIG. 1 is an in situ UV-vis test chart of a comparative perovskite thin film, ionic liquid MAAc-modified perovskite thin film and ionic liquid MAFA-modified perovskite thin film.
FIG. 2 is a theoretical calculation of MAAc modified perovskite thin film.
FIG. 3 is a photograph showing a comparison of perovskite thin film of comparative example and perovskite thin film after modification with ionic liquid MAAc.
Detailed Description
The invention provides a perovskite solar cell and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and are further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a preparation method of a perovskite solar cell, which comprises the following steps:
(1) Providing a conductive substrate;
(2) Preparing an electron transport layer on the conductive substrate;
(3) Preparing a perovskite layer on the surface of the electron transport layer, wherein the perovskite layer comprises a perovskite body and MAAc;
(4) Preparing a hole transport layer on the surface of the perovskite layer;
(5) And preparing an electrode on the surface of the hole transport layer.
In the embodiment, trace ionic liquid MAAc is added in the perovskite layer, and the MAAc can passivate and fill internal and surface defects of the perovskite layer, so that non-radiative recombination of photogenerated carriers is reduced, and the photoelectric conversion efficiency of the device is effectively improved.
In one embodiment, the mass ratio of the MAAc in the perovskite layer is 0.05-1%. A proper trace amount of MAAc can effectively passivate defects inside the perovskite, and excessive amount of MAAc ionic liquid may cause the perovskite to be difficult to convert.
In one embodiment, the perovskite body is ABX 3 Wherein a comprises a methylamine cation, a formamidine cation, and a cesium cation, or a comprises a methylamine cation, a formamidine cation, and a potassium cation; b comprises lead cations; x includes chloride, bromide and iodide anions.
In step (1), in one embodiment, the conductive substrate may be, but is not limited to, a transparent conductive substrate such as an ITO substrate, an FTO substrate, or the like.
In one embodiment, the conductive substrate is a cleaning-treated and UV-treated conductive substrate. Specifically, firstly, conducting a cleaning treatment on a conductive substrate; and then carrying out UV treatment on the cleaned conductive substrate to improve the hydrophilicity of the conductive substrate. Wherein, the step of cleaning can be: and sequentially adopting a mixed solution of deionized water and detergent, deionized water, ethanol and isopropanol to ultrasonically clean the conductive substrate, and then drying by nitrogen.
In step (2), in one embodiment, the step of preparing an electron transport layer on the conductive substrate specifically includes:
preparing an electron transport material solution (such as tin dioxide solution, titanium dioxide solution and the like);
and coating the electron transport material solution on a conductive substrate by a solution method (such as a spin coating method and the like), and annealing to obtain the electron transport layer.
In step (3), in one embodiment, the step of preparing a perovskite layer on the surface of the electron transport layer specifically includes:
providing a mixed solution of lead iodide and MAAc, and providing an organic halide solution;
spin-coating the mixed solution of lead iodide and MAAc on the surface of the electron transport layer, and performing a first annealing treatment to obtain a lead iodide layer;
and spin-coating the organic halide solution on the surface of the lead iodide layer, and carrying out second annealing treatment to obtain the perovskite layer.
In this example, the perovskite layer solution was configured in two parts, namely a mixed solution of lead iodide and MAAc and an organic halide solution. After weighing the medicines, respectively adding solvents, and uniformly dissolving to respectively obtain a mixed solution of lead iodide and MAAc and an organic halide solution. And respectively performing spin coating and annealing operation to obtain the perovskite layer. Namely, the perovskite layer was prepared by the two-step spin coating method in this example.
In one embodiment, the mixed solution of lead iodide and MAAc consists of lead iodide, MAAc and solvent, and the addition amounts of the lead iodide, the MAAc and the solvent are respectively 0.5-3 mol, 0.5-50 mu L and 950-999.5 mL.
In the embodiment, trace ionic liquid MAAc is added into the perovskite layer, and the MAAc can passivate and fill internal and surface defects of the perovskite layer, so that perovskite conversion is promoted. Compared with a perovskite layer without adding ionic liquid and a perovskite layer with adding ionic body fluid methylamine formic acid (MAFA), the perovskite layer added with ionic liquid MAAc in the embodiment has higher conversion efficiency and greatly shortens conversion time. Particularly, the MAAc can promote the uniform and rapid film formation of perovskite with large area due to the adoption of a two-step method.
In one embodiment, the method for preparing the mixed solution of lead iodide and MAAc comprises the following steps:
dissolving lead iodide in a solvent to obtain a lead iodide solution;
adding MAAc into the lead iodide solution to obtain a mixed solution of lead iodide and MAAc; wherein the solvent can be one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), etc. It should be noted that the solvent is a polar solvent, and evaporates during annealing, while the ionic liquid MAAc has small vapor pressure and does not volatilize, so that the perovskite layer containing trace ionic liquid MAAc can be finally obtained.
In one embodiment, in the step of spin-coating the mixed solution of lead iodide and MAAc on the surface of the electron transport layer, the spin-coating parameters include: the rotating speed is 1000-4000r/s and the time is 20-60s. Further, the rotation speed was 2000r/s and the time was 30s.
In one embodiment, the parameters of the first annealing treatment (performed in a glove box inert atmosphere environment) include: the temperature is 40-90 ℃ and the time is 10-120s. Further, the temperature was 70℃and the time was 60s.
In one embodiment, the organic halide solution may be a FAI, MACl, MABr and CsI-containing solution, wherein the solvent may be IPA or the like, but is not limited thereto; alternatively, the organic halide solution may be a FAI, MACl, MABr and KI-containing solution, wherein the solvent may be IPA or the like, but is not limited thereto. Mixed cationic perovskite is employed because of its lower bandgap, which is beneficial for improving the efficiency of the device. This example also incorporates Cs in the perovskite layer + Or K + The Cs is + Or K + The perovskite phase formation can be promoted, and the secondary phase formation can be suppressed.
Further, the mass ratio of FAI, MACl, MABr, csI is 60 (6-10): 1-2; or the mass ratio of FAI, MACl, MABr, KI is 60 (6-10): 1-2.
In one embodiment, in the step of spin-coating the organic halide solution onto the surface of the lead iodide layer, the spin-coating parameters include: the rotating speed is 1000-4000r/s and the time is 20-60s. Further, the rotation speed was 2000r/s and the time was 30s.
In one embodiment, the parameters of the second annealing process (performed in a dry box environment) include: the temperature is 90-130 ℃ and the time is 10-80min. Further, the temperature was 100℃and the time was 50min.
In step (4), a hole transport layer is prepared. In one embodiment, the step of preparing a hole transport layer on the surface of the perovskite layer specifically includes:
providing a hole transport material solution;
and coating the hole transport material solution on the surface of the perovskite layer by a solution method (such as a spin coating method and the like), and forming the hole transport layer through annealing treatment.
In one embodiment, the hole transport material solution may be, but is not limited to, one of a Spiro-ome solution, PTAA solution, and the like.
In step (5), an electrode is prepared. And preparing a metal electrode on the surface of the hole transport layer by an evaporation method, and finally obtaining the perovskite solar cell.
The embodiment of the invention provides a perovskite solar cell, which is prepared by adopting the method disclosed by the embodiment of the invention.
The invention is further illustrated by the following specific examples.
In the following examples, materials such as ITO, FTO, lead iodide, iodoformamidine (FAI), methyl chloride (MACl), cesium iodide, potassium iodide, methyl amine, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, sprio-OMeTAD, etc. are all commercially available products.
1. Preparation of MAAc modified perovskite thin film:
preparing a solution of the perovskite layer. 1.5mol of lead iodide was dissolved in 990mL of DMF solution, followed by the addition of 10. Mu.L of ionic liquid MAAc to give a mixed solution of lead iodide and ionic liquid MAAc. FAI, MACl, MABr, csI is dissolved in IPA solution and stirred uniformly to obtain organic halide solution; wherein the mass concentration of FAI, MACl, MABr, csI is 60mg/mL, 10mg/mL and 1mg/mL respectively.
The preparation of the perovskite layer is divided into two steps. The first step: setting parameters of a spin coater: the revolution was 1500r/s and run for 30s. And (3) dripping the mixed solution of lead iodide and the ionic liquid MAAc on the surface of the substrate, starting a spin coater, and cooling for standby after annealing at 70 ℃ for 60 seconds after spin coating is finished. And a second step of: on the basis of the first step, an organic halide solution was added dropwise, and the spin Tu Yi parameters were the same as those of the first step. After spin coating, the sample is placed on a heating table, annealed at 100 ℃ for 50min, and then prepared at room temperature.
2. Preparation of MAFA modified perovskite thin film: the same as the preparation of the MAAc modified perovskite thin film only differs in that: the ionic liquid MAAc was replaced with ionic liquid MAFA.
3. Preparation of perovskite thin film of comparative example: the same as the preparation of the MAAc modified perovskite thin film only differs in that: no ionic liquid MAAc was added.
Control is shown in FIGS. 1 (a) - (c), respectivelyIn-situ UV-vis graphs of MAAc modified and MAFA modified perovskite film samples show that the perovskite film after MAAc modification is more rapidly transformed and faster crystallization kinetics process is shown. In FIG. 2 (a) is perovskite MAPbI 3 (b) is acetate ion CH 3 COO - For MAPbI 3 The crystal structure of filling iodine vacancies in bulk phase, (c) is the density of states distribution diagram corresponding to the crystal structure of figure (a), and (d) is the density of states distribution diagram corresponding to the crystal structure of figure (b). The conversion efficiency of the perovskite film modified by the ionic body fluid MAAc is higher, the conversion time is only about 15s, and the conversion time of the control and MAFA is about 30s and 20s respectively. Through theoretical calculation, MAAc is shown to be capable of effectively filling the defects in perovskite, and is shown in fig. 2. Fig. 3 (a) is a photograph of a perovskite film of a control example, fig. 3 (b) is a photograph of a perovskite film modified with an ionic liquid MAAc, and fig. 3 shows that the MAAc-modified perovskite film is more uniform, while the control film sample shows unconverted dark yellow edges.
Example 1: the preparation method of the perovskite solar cell of the embodiment comprises the following steps:
(1) Cleaning and UV treatment of the ITO substrate. Firstly, placing an ITO substrate into a beaker, ultrasonically cleaning the ITO substrate for 30min in deionized water and a detergent solution, then ultrasonically cleaning the ITO substrate for 30min in deionized water, then ultrasonically cleaning the ITO substrate for 30min in an ethanol solution, finally ultrasonically cleaning the ITO substrate for 30min in an isopropanol solution, and drying the ITO substrate by adopting nitrogen after the completion of ultrasonic cleaning. Placing the cleaned ITO substrate in a UV instrument, and carrying out ozone treatment for 20min.
(2) The tin dioxide electron transport layer (thickness 50 nm) was prepared by spin coating. Preparing a tin dioxide solution (the tin dioxide solution is diluted by deionized water, and the volume ratio of the tin dioxide solution to the deionized water solution is 1:5). Setting parameters of a spin coater: the revolution was 4000r/s and run for 30s. And (3) dripping the tin dioxide solution on the surface of the ITO substrate subjected to the UV treatment, starting a spin coater, and after spin coating is finished, placing the sample on a heating table for annealing at 150 ℃ for 30min.
(3) The perovskite layer (thickness is 700 nm) is prepared by a two-step spin coating method, and the specific preparation steps are as follows:
preparing a solution of the perovskite layer. 1.5mol of lead iodide was dissolved in 990mL of DMF solution, followed by the addition of 10. Mu.L of ionic liquid MAAc to give a mixed solution of lead iodide and ionic liquid MAAc. FAI, MACl, MABr, csI is dissolved in IPA solution and stirred uniformly to obtain organic halide solution; wherein the mass concentration of FAI, MACl, MABr, csI is 60mg/mL, 10mg/mL and 1mg/mL respectively.
The preparation of the perovskite layer is divided into two steps. The first step: and carrying out UV treatment on the ITO substrate with the electron transport layer on the surface for 20min. Setting parameters of a spin coater: the revolution was 1500r/s and run for 30s. And (3) dripping the mixed solution of lead iodide and the ionic liquid MAAc on the surface of the electron transport layer, starting a spin coater, and cooling for standby after the spin coating is finished and annealing at 70 ℃ for 60 seconds. And a second step of: on the basis of the first step, an organic halide solution was added dropwise, and the spin Tu Yi parameters were the same as those of the first step. After spin coating, the sample is placed on a heating table, annealed at 100 ℃ for 50min and cooled for standby.
(4) The spiral-OMeTAD hole transport layer (thickness 200 nm) was prepared using spin-coating process. Spin coating was performed using a Spiro-OMeTAD solution, which was prepared as follows: 70mg of Spiro-OMeTAD, 40. Mu.L of TBP (tributyl phosphate), 10. Mu.L of Li-TFSI solution (wherein the solvent is acetonitrile, liTFSI 260mg, acetonitrile 1 mL) were mixed in 1mL of chlorobenzene. Setting parameters of a spin coater: the revolution was 4000r/s and run for 30s. And (3) dripping the Spiro-OMeTAD solution on the surface of the perovskite layer, starting a spin coater, and standing for one night for oxidization after spin coating to obtain the hole transport layer.
(5) And (3) evaporating a gold electrode with the thickness of about 100nm on the surface of the hole transport layer to obtain the perovskite solar cell.
Example 2: the preparation method of the perovskite solar cell of the embodiment comprises the following steps:
(1) Cleaning and UV treatment of the ITO substrate. Firstly, placing an ITO substrate into a beaker, ultrasonically cleaning the ITO substrate for 30min in deionized water and a detergent solution, then ultrasonically cleaning the ITO substrate for 30min in deionized water, then ultrasonically cleaning the ITO substrate for 30min in an ethanol solution, finally ultrasonically cleaning the ITO substrate for 30min in an isopropanol solution, and drying the ITO substrate by adopting nitrogen after the completion of ultrasonic cleaning. Placing the cleaned ITO substrate in a UV instrument, and carrying out ozone treatment for 20min.
(2) The tin dioxide electron transport layer (thickness 50 nm) was prepared by spin coating. Preparing a tin dioxide solution (the volume ratio of the tin dioxide solution to the deionized water solution is 1:6). Setting parameters of a spin coater: the revolution was 3000r/s and run for 30s. And (3) dripping the tin dioxide solution on the surface of the ITO substrate subjected to the UV treatment, starting a spin coater, and after spin coating is finished, placing the sample on a heating table for annealing at 150 ℃ for 60min.
(3) The perovskite layer (thickness is 700 nm) is prepared by a two-step spin coating method, and the specific preparation steps are as follows:
preparing a solution of the perovskite layer. 1.5mol of lead iodide was dissolved in 970mL of DMF solution, followed by addition of 30. Mu.L of ionic liquid MAAc to give a mixed solution of lead iodide and ionic liquid MAAc. FAI, MACl, MABr, KI is dissolved in IPA solution and stirred uniformly to obtain organic halide solution; wherein the mass concentration of FAI, MACl, MABr, KI is 60mg/mL, 6mg/mL and 1mg/mL respectively.
The perovskite active layer is prepared in two steps. The first step: and carrying out UV treatment on the ITO substrate with the electron transport layer on the surface for 20min. Setting parameters of a spin coater: the revolution was 2000r/s and run for 30s. And (3) dripping the mixed solution of lead iodide and the ionic liquid MAAc on the surface of the electron transport layer, starting a spin coater, and cooling for standby after the spin coating is finished and annealing at 70 ℃ for 80 seconds. And a second step of: on the basis of the first step, an organic halide solution was added dropwise, and the spin Tu Yi parameters were the same as those of the first step. After spin coating, the sample is placed on a heating table, annealed at 110 ℃ for 40min and cooled for standby.
(4) The spiral-OMeTAD hole transport layer (thickness 200 nm) was prepared using spin-coating process. Spin coating was performed using a Spiro-OMeTAD solution, which was prepared as follows: 70mg of Spiro-OMeTAD, 40. Mu.L of TBP (tributyl phosphate), 10. Mu.L of Li-TFSI solution (wherein the solvent is acetonitrile, liTFSI 260mg, acetonitrile 1 mL) were mixed in 1mL of chlorobenzene. Setting parameters of a spin coater: the revolution was 4000r/s and run for 30s. And (3) dripping the Spiro-OMeTAD solution on the surface of the perovskite layer, starting a spin coater, and standing for one night for oxidization after spin coating to obtain the hole transport layer.
(5) And (3) evaporating a gold electrode with the thickness of about 100nm on the surface of the hole transport layer to obtain the perovskite solar cell.
Example 3: the preparation method of the perovskite solar cell of the embodiment comprises the following steps:
(1) FTO substrate cleaning and UV treatment. Firstly placing an FTO substrate into a beaker, ultrasonically cleaning the FTO substrate for 30min in deionized water and detergent solution, then ultrasonically cleaning the FTO substrate for 30min in deionized water, then ultrasonically cleaning the FTO substrate for 30min in ethanol solution, finally ultrasonically cleaning the FTO substrate for 30min in isopropanol solution, and drying the FTO substrate by adopting nitrogen after completion. Placing the cleaned FTO substrate in a UV instrument, and carrying out ozone treatment for 20min.
(2) The tin dioxide electron transport layer (thickness 50 nm) was prepared by spin coating. Preparing a tin dioxide solution (the volume ratio of the tin dioxide solution to the deionized water solution is 1:5). Setting parameters of a spin coater: the revolution was 4000r/s and run for 40s. And (3) dripping the tin dioxide solution on the surface of the FTO substrate subjected to the UV treatment, starting a spin coater, and after spin coating is finished, placing the sample on a heating table for annealing at 150 ℃ for 30min.
(3) The perovskite layer (thickness is 700 nm) is prepared by a two-step spin coating method, and the specific preparation steps are as follows:
preparing a solution of the perovskite layer. 1.5mol of lead iodide was dissolved in a mixed solution of 900mL of DMF and 50mL of DMSO, and then 50. Mu.L of ionic liquid MAAc was added to obtain a mixed solution of lead iodide and ionic liquid MAAc. FAI, MACl, MABr, csI is dissolved in IPA solution and stirred uniformly to obtain organic halide solution; wherein the mass concentration of FAI, MACl, MABr, csI is 60mg/mL, 8mg/mL and 2mg/mL respectively.
The preparation of the perovskite layer is divided into two steps. The first step: and carrying out UV treatment on the FTO substrate with the electron transport layer on the surface for 20min. Setting parameters of a spin coater: the revolution was 1500r/s and run for 40s. And (3) dripping the mixed solution of lead iodide and the ionic liquid MAAc on the surface of the electron transport layer, starting a spin coater, and cooling for standby after the spin coating is finished and annealing at 70 ℃ for 60 seconds. And a second step of: on the basis of the first step, an organic halide solution was added dropwise, and the spin Tu Yi parameters were the same as those of the first step. After spin coating, the sample is placed on a heating table, annealed at 90 ℃ for 50min and cooled for standby.
(4) The spiral-OMeTAD hole transport layer (thickness 200 nm) was prepared using spin-coating process. Spin coating was performed using a Spiro-OMeTAD solution, which was prepared as follows: 70mg of Spiro-OMeTAD, 40. Mu.L of TBP (tributyl phosphate), 10. Mu.L of Li-TFSI solution (wherein the solvent is acetonitrile, liTFSI 260mg, acetonitrile 1 mL) were mixed in 1mL of chlorobenzene. Setting parameters of a spin coater: the revolution was 4000r/s and run for 30s. And (3) dripping the Spiro-OMeTAD solution on the surface of the perovskite layer, starting a spin coater, and standing for one night for oxidization after spin coating to obtain the hole transport layer.
(5) And (3) evaporating a gold electrode with the thickness of about 100nm on the surface of the hole transport layer to obtain the perovskite solar cell.
Example 4: the preparation method of the perovskite solar cell of the embodiment comprises the following steps:
(1) Cleaning and UV treatment of the ITO substrate. Firstly, placing an ITO substrate into a beaker, ultrasonically cleaning the ITO substrate for 30min in deionized water and a detergent solution, then ultrasonically cleaning the ITO substrate for 30min in deionized water, then ultrasonically cleaning the ITO substrate for 30min in an ethanol solution, finally ultrasonically cleaning the ITO substrate for 30min in an isopropanol solution, and drying the ITO substrate by adopting nitrogen after the completion of ultrasonic cleaning. Placing the cleaned ITO substrate in a UV instrument, and carrying out ozone treatment for 20min.
(2) The tin dioxide electron transport layer (thickness 50 nm) was prepared by spin coating. Preparing a tin dioxide solution (the volume ratio of the tin dioxide solution to the deionized water solution is 1:6). Setting parameters of a spin coater: the revolution was 3000r/s and run for 30s. And (3) dripping the tin dioxide solution on the surface of the ITO substrate subjected to the UV treatment, starting a spin coater, and after spin coating is finished, placing the sample on a heating table for annealing at 150 ℃ for 30min.
(3) The perovskite layer (thickness is 700 nm) is prepared by a two-step spin coating method, and the specific preparation steps are as follows:
preparing a solution of the perovskite layer. 1.5mol of lead iodide was dissolved in 990mL of NMP solution, followed by addition of 10. Mu.L of ionic liquid MAAc to give a mixed solution of lead iodide and ionic liquid MAAc. FAI, MACl, MABr, KI is dissolved in IPA solution and stirred uniformly to obtain organic halide solution; wherein the mass concentration of FAI, MACl, MABr, KI is 60mg/mL, 10mg/mL and 2mg/mL respectively.
The preparation of the perovskite layer is divided into two steps. The first step: and carrying out UV treatment on the ITO substrate with the electron transport layer on the surface for 20min. Setting parameters of a spin coater: the revolution was 1500r/s and run for 30s. And (3) dripping the mixed solution of lead iodide and the ionic liquid MAAc on the surface of the substrate, starting a spin coater, and cooling for standby after annealing at 70 ℃ for 60 seconds after spin coating is finished. And a second step of: on the basis of the first step, an organic halide solution was added dropwise, and the spin Tu Yi parameters were the same as those of the first step. After spin coating, the sample is placed on a heating table, annealed at 100 ℃ for 50min and cooled for standby.
(4) The spiral-OMeTAD hole transport layer (thickness 200 nm) was prepared using spin-coating process. Spin coating was performed using a Spiro-OMeTAD solution, which was prepared as follows: 70mg of Spiro-OMeTAD, 40. Mu.L of TBP (tributyl phosphate), 10. Mu.L of Li-TFSI solution (wherein the solvent is acetonitrile, liTFSI 260mg, acetonitrile 1 mL) were mixed in 1mL of chlorobenzene. Setting parameters of a spin coater: the revolution was 4000r/s and run for 30s. And (3) dripping the Spiro-OMeTAD solution on the surface of the perovskite layer, starting a spin coater, and standing for one night for oxidization after spin coating to obtain the hole transport layer.
(5) And (3) evaporating a gold electrode with the thickness of about 100nm on the surface of the hole transport layer to obtain the perovskite solar cell.
The perovskite solar cells prepared in examples 1 to 4 were subjected to a photoelectric conversion efficiency test using a steady-state calibrated solar simulator, and the test results are shown in table 1. From table 1, it is known that the photoelectric conversion efficiency can be effectively improved by adding a small amount of ionic liquid MAAc into perovskite.
Table 1 properties of perovskite solar cells prepared in each example
Figure BDA0003631672950000131
Figure BDA0003631672950000141
In summary, the invention provides a perovskite solar cell and a preparation method thereof. Cesium is added in the perovskite layerIon (Cs) + ) Or potassium ion (K) + ) And trace ionic liquid methylamine acetic acid (MAAc), and preparing the perovskite layer by using a two-step spin coating method. Wherein Cs + Or K + The perovskite phase formation can be promoted, and the secondary phase formation can be suppressed. The trace ionic liquid MAAc is added into the perovskite layer to passivate and fill the internal and surface defects of the perovskite layer, so that the perovskite conversion is promoted. In addition, compared with a control perovskite film and an ionic humoral methylamine carboxylic acid (MAFA) modified perovskite film, the perovskite film modified by ionic humoral MAAc has higher conversion efficiency and shorter conversion time by virtue of an in-situ UV-vis characterization technology. Besides improving the stability and photoelectric conversion efficiency of the prepared modified perovskite device, the effective regulation and control of MAAc on the defect state of the perovskite is verified by means of a first principle from the aspect of mechanism. Especially for the industrial production of the two-step method, MAAc can promote the uniform and rapid film formation of perovskite with large area.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (6)

1. A method of fabricating a perovskite solar cell, comprising the steps of:
providing a conductive substrate;
preparing an electron transport layer on the conductive substrate;
preparing a perovskite layer on the surface of the electron transport layer, wherein the perovskite layer comprises a perovskite body and MAAc;
preparing a hole transport layer on the surface of the perovskite layer;
preparing an electrode on the surface of the hole transport layer;
in the perovskite layer, the mass ratio of the MAAc is 0.05-1%;
the method for preparing the perovskite layer on the surface of the electron transport layer comprises the following steps:
providing a mixed solution of lead iodide and MAAc, and providing an organic halide solution;
spin-coating the mixed solution of lead iodide and MAAc on the surface of the electron transport layer, and performing a first annealing treatment to obtain a lead iodide layer;
spin-coating the organic halide solution on the surface of the lead iodide layer, and carrying out second annealing treatment to obtain the perovskite layer;
the mixed solution of lead iodide and MAAc consists of lead iodide, MAAc and a solvent, wherein the addition amounts of the lead iodide, the MAAc and the solvent are respectively 0.5-3 mol, 0.5-50 mu L and 950-999.5 mL;
the preparation method of the mixed solution of lead iodide and MAAc comprises the following steps:
dissolving lead iodide in a solvent to obtain a lead iodide solution;
adding MAAc into the lead iodide solution to obtain a mixed solution of lead iodide and MAAc;
wherein the solvent is one or more than two of N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone;
in the step of spin-coating the mixed solution of lead iodide and MAAc on the surface of the electron transport layer, the spin-coating parameters include: the rotating speed is 1000-4000r/s, and the time is 20-60s; the parameters of the first annealing treatment include: the temperature is 40-90 ℃ and the time is 10-120s.
2. The method for producing a perovskite solar cell according to claim 1, wherein,
the perovskite body is ABX 3 Wherein a comprises a methylamine cation, a formamidine cation, and a cesium cation, or a comprises a methylamine cation, a formamidine cation, and a potassium cation; b comprises lead cations; x includes chloride, bromide and iodide anions.
3. The method of manufacturing a perovskite solar cell according to claim 1, wherein the organic halide solution is a FAI, MACl, MABr and CsI containing solution; alternatively, the organic halide solution is a FAI, MACl, MABr and KI containing solution.
4. A method of manufacturing a perovskite solar cell according to claim 3, wherein the mass ratio of FAI, MACl, MABr, csI is 60 (6-10): (6-10): (1-2); or the mass ratio of FAI, MACl, MABr, KI is 60 (6-10): 1-2.
5. The method of manufacturing a perovskite solar cell according to claim 1, wherein in the step of spin-coating the organic halide solution on the surface of the lead iodide layer, the spin-coating parameters include: the rotating speed is 1000-4000r/s, and the time is 20-60s;
and/or, the parameters of the second annealing treatment comprise: the temperature is 90-130 ℃ and the time is 10-80min.
6. A perovskite solar cell prepared by the method of any one of claims 1-5.
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