CN113725367A - Solar cell device based on 2D-PVK synergistic co-passivation perovskite thin film grain boundary and surface defects and preparation method - Google Patents
Solar cell device based on 2D-PVK synergistic co-passivation perovskite thin film grain boundary and surface defects and preparation method Download PDFInfo
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- 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
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
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- H—ELECTRICITY
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention provides a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundaries and surface defects and a preparation method thereof. The solar cell device comprises a conductive substrate, an electron transport layer, an organic-inorganic hybrid metal halide perovskite light absorption layer, a cooperative passivation layer, a hole transport layer and a metal electrode layer which are sequentially prepared. The solar photovoltaic device of the metal halide perovskite thin film is simple in preparation method and low in cost, the 2D-PVK cooperative passivation layer effectively passivates the crystal boundary defects and the surface defects of the perovskite thin film, the non-radiative recombination loss caused by the defects is greatly reduced, the photoelectric conversion efficiency and the long-term stability of the device are improved, and important theoretical basis and technical support are provided for the practicability of the high-efficiency stable perovskite solar cell.
Description
Technical Field
The invention relates to a semiconductor material photovoltaic technology, in particular to a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundary and surface defects and a preparation method thereof
Background
In recent years, Perovskite Solar Cells (PS for short) have been developedCs) is raised and developed rapidly, is expected to break through the existing principle and technical limitation, provides a revolutionary technical support for the development and utilization of clean solar energy, and is greatly concerned by the academic and industrial fields. The metal halide perovskite material is used as a direct band gap semiconductor material and has a perovskite crystal form ABX3(A＝MA+(CH3NH3 +)、FA+(NH(CH3)2 +)、Cs+Etc., B ═ Pb2+、Sn2+Etc., X ═ I-、Br-、Cl-) And a series of excellent photoelectric characteristics, such as long carrier diffusion, high extinction coefficient, adjustable band gap, high defect tolerance and the like, and can be grown by a simple low-cost solution method, so that the photoelectric material has great brilliance in the field of photoelectric devices. Today, small area single junction PSCs have recorded as high as 25.5% Photoelectric Conversion Efficiency (PCE).
Currently, PSCs have become the leaders for low-cost, high-efficiency solar cells. However, the device stability is still very different from the commercial application standard, which seriously hinders the large-scale industrialization process. A number of studies have shown that PCE losses and operational instability of PSCs are closely related to the nonradiative annihilation of carriers. Reducing non-radiative recombination losses and suppressing interface degradation by passivating defects is a major strategy to improve the optoelectronic performance and stability of PSCs. Therefore, the important point of basic research in the field of the PSCs at present is to deeply research the influence mechanism of the defects on the stability of the PSCs and provide countermeasures so as to greatly reduce the energy loss caused by non-radiative recombination.
In view of the negative influence of defects on the performance and stability of PSCs devices, researchers have proposed many effective strategies from the passivation point of view, which can be roughly classified into the following three categories: (i) anions or metal cations are doped to passivate point defects in the perovskite film so as to enhance the stability of the perovskite layer under the working condition; (ii) the stability of a perovskite layer and the interface related to the perovskite layer is improved by introducing alkylammonium halide or Lewis acid-base passivation to the grain boundary or surface defect of the perovskite film; (iii) using PbI2Self-passivating effect of or introduction of wide band gap materials to passivate perovskitesInterface defects between the thin film and the charge transport layer (ETL and HTL) improve interface stability under operating conditions.
Disclosure of Invention
The invention aims to provide a solar cell device based on 2D-PVK (two-dimensional-polyvinyl-k) synergistic co-passivation of a perovskite thin film grain boundary and surface defects, aiming at the problem of non-radiative coincident loss of a current carrier caused by the grain boundary and surface defects of an organic-inorganic metal halide perovskite thin film, and the solar cell device has excellent efficiency and stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
a solar cell device based on 2D-PVK cooperative co-passivation of perovskite thin film grain boundaries and surface defects comprises a conductive substrate, an electron transport layer, an organic-inorganic hybrid metal halide perovskite light absorption layer, a cooperative passivation layer, a hole transport layer and a metal electrode layer, wherein the electron transport layer, the organic-inorganic hybrid metal halide perovskite light absorption layer, the cooperative passivation layer, the hole transport layer and the metal electrode layer are sequentially prepared; the conductive substrate is indium tin oxide conductive glass; the electron transport layer is SnO2Sol-gel with a thickness of 25-35 nm; the light absorption layer of the organic-inorganic hybrid metal halide perovskite is FAPbI3Perovskite thin film layer, FAPbI3The 2D material is present at the grain boundaries of the perovskite thin film layer and is present at FAPBI3The surface of the perovskite thin film layer is provided with a PVK thin layer, FAPBI3The thickness of the perovskite thin film layer is 400-600 nm, and the thickness of the PVK thin film layer is 3-5 nm; the hole transport layer is a solid electrolyte Spiro-OMeTAD layer, and the thickness of the hole transport layer is 150-200 nm; the photo-anode is a metal thin film layer, and the thickness of the photo-anode is 50-70 nm.
A preparation method of a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundaries and surface defects comprises the following steps: an electron transport layer, an organic-inorganic hybrid metal halide perovskite light absorption layer and a hole transport layer are sequentially grown on a conductive substrate by adopting an all-solution method, and a gold electrode is evaporated on the hole transport layer to prepare the solar cell device based on 2D-PVK synergistic co-passivation perovskite thin film grain boundary and surface defects;
the preparation method of the electron transport layer comprises the following steps: SnCl2·2H2O and anhydrousEthanol is mixed according to a mass ratio of 1: 116-118, sealing with a sealing film, wrapping with tinfoil to prevent light, standing at room temperature for 24 hours to obtain transparent and uniform SnO2Sol-gel, which is filtered by a filter head with the diameter of 0.2 μm before use; preparing by adopting a single-step spin coating method, starting a spin coater, setting 3000 revolutions for 30s, placing the conductive substrate after ozone treatment on a rotary bracket of the spin coater, fixing the conductive substrate by vacuum adsorption, and carrying out SnO treatment2Dropping the sol-gel in the center of the conductive substrate, starting a spin coater, moving the sample to a hot plate at 145-155 ℃ after the spin coater stops rotating, annealing for 25-35 min, moving the sample to a metal heat conducting plate after annealing, cooling the sample to room temperature, and improving SnO2The coverage rate of the film is repeated once again by the same spin coating process, the sample is firstly moved to a hot plate at 145-155 ℃ for annealing for 5-7 min, the sample is cooled to room temperature and then is annealed on the hot plate at 145-155 ℃ for 110-130 min to obtain SnO2An ITO sample; wherein, 45 μ L of SnO2The sol-gel has an area of 1.5 × 1.5cm corresponding to the conductive substrate2；
The preparation method of the organic-inorganic hybrid metal halide perovskite light absorption layer comprises the following steps: and (2) mixing the following components in percentage by mass: 810: 223 FPEAI, HC (NH)2)2I and PbI2Dissolving the precursor solution in a mixed solution of N-methyl-2-propiophenone and N, N-dimethylformamide with the volume mass ratio of 65 mu L to 3000mg, sealing the solution with a sealing film, and stirring the solution for 5 to 10 minutes by using an electric stirrer to obtain a precursor solution of the perovskite precursor solution; dissolving PVK in chlorobenzene to obtain a chlorobenzene solution of PVK with the concentration of 1mg/mL, stirring for more than 10 hours at room temperature, and standing for 12 hours at room temperature to obtain a transparent and uniform perovskite precursor solution; the preparation method is characterized in that a one-step spin coating method is adopted, and the perovskite precursor solution is uniformly coated on SnO treated by ozone for 15-25 min2On an ITO sample, setting a spin coater to rotate for 30s at 4000 times; dripping the PVK chlorobenzene solution on the rotating SnO at a stable and uniform speed within 15-17 s from the end of rotation2On an ITO sample, after the spin coater stops rotating, the sample is moved to a hot plate at 145-155 ℃, annealing is carried out for 20-25 min, and after annealing, the sample is moved to a metal heat conducting plate and cooled to room temperature to obtain PVK-2Dperovskite/SnO2An ITO sample; wherein the area of the conductive substrate is related to the chlorobenzene solution of PVKThe method comprises the following steps: 180-200 μ L for 1.5X 1.5cm2A conductive substrate;
the preparation method of the hole transport layer comprises the following steps: the mass-to-volume ratio of the hole transport material Spiro-OMeTAD to the chlorobenzene solution is 343 mg: 4mL of the solution is mixed, and then 4-tert-butylpyridine and a lithium bistrifluoromethanesulfonylimide solution are sequentially added; chlorobenzene solution: 4-tert-butylpyridine: the volume ratio of the lithium bistrifluoromethanesulfonylimide solution is 4000: 135: 77; the preparation method adopts a single-step spin coating method, a spin coating machine is started, 3000 revolutions are set for 30s, and PVK-2D perovskite/SnO is put2The ITO sample is placed on a rotary bracket of a spin coater and fixed through vacuum adsorption, the spin coater is started, and the Spiro-OMeTAD solution is stably dripped on the rotating PVK-2D perovskite/SnO at a constant speed within 18-20 s from the end of rotation2Stopping rotating the spin coater on the ITO sample to obtain a hole transport layer; wherein, the relationship between the area of the Spiro-OMeTAD solution and the area of the conductive substrate is as follows: 15 μ L for 1.5X 1.5cm2A conductive substrate;
finally, the gold electrode is evaporated to obtain the structure of Au/Spiro-OMeTAD/PVK-2Dperovskite/SnO2ITO based organic-inorganic hybrid metal halide perovskite solar cell device based on PVA passivation film surface/interface defects, namely the solar cell device based on 2D-PVK synergistic co-passivation perovskite film grain boundary and surface defects.
The invention has the beneficial effects that:
1) the invention discloses a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundary and surface defects, which is characterized in that an electron injection layer (SnO) is sequentially grown on a conductive ITO substrate by adopting a full low-temperature solution method2) Perovskite light absorption layers and hole injection layers (Spiro-OMeTAD). The carrier life of 618ns is measured at room temperature by the PSCs prepared by the method; meanwhile, the PSCs show excellent photoelectric conversion characteristics, compared with 16.5% of PCE of a comparison device, the efficiency of the device after 2D-PVK synergistic modification and passivation is up to 21.6%, and the increase is 5 percentage points; the 2D-PVK synergistically modified passivation layer greatly reduces the grain boundary and interface defect state density of the perovskite thin film, is very beneficial to the light working stability of PSCs (polymer dispersed semiconductor) devices, and is contrasted with the devices after continuous light irradiation for 800 hoursThe efficiency is only 16% of the initial efficiency, and the efficiency of the device after 2D-PVK synergistic modification and passivation can still keep more than 84% of the initial efficiency. In view of the advantages of the PSCs, the excellent efficiency and stability will inevitably expand its application area.
2) The invention creates a method for entering a cooperative passivation layer, which comprises the following steps: on the premise of not increasing a device preparation program, a 2D-PVK cooperative passivation layer is introduced, and the problem of carrier non-radiative coincidence loss caused by perovskite thin film grain boundaries and surface defects is solved by utilizing the passivation effect of a 2D material on the perovskite thin film grain boundary defects and the passivation effect of PVK blunt perovskite thin film surface defects, so that the efficiency of PCSs is improved, and the stability problem is solved.
3) The invention relates to a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundaries and surface defects, and the preparation and passivation methods of the solar cell device are simple and feasible in process and low in cost.
Drawings
FIG. 1 is a cross-sectional SEM image of a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundaries and surface defects;
FIG. 2 is a Transmission Electron Microscope (TEM) image of a perovskite thin film containing 3.5 mol% 2D material. The areas I and II marked in a were investigated for enlargement in b and c, respectively, and the insets in b and c are fourier transform (FFT) plots;
FIG. 3 is a perovskite thin film of a control and synergistically passivated with 2D-PVK: a is an X-ray diffraction (XRD) pattern; b is a time-resolved PL decay curve, and the carrier life before and after 2D-PVK synergistic passivation modification obtained through double-index fitting calculation is 135 ns and 618ns respectively;
FIG. 4 is a current-voltage (J-V) curve of a control and PSCs after 2D-PVK synergistic passivation;
FIG. 5 is a graph of the stable output efficiency of the control and PSCs after 2D-PVK co-passivation;
FIG. 6 is a plot of Transient Photovoltage (TPV) decay for a control and PSCs after 2D-PVK synergistic passivation;
FIG. 7 is a graph of the photoelectric conversion efficiency of the control sample and PSCs after 2D-PVK synergistic passivation under continuous illumination (90. + -. 10 mWcm)-2) Evolution ofA process;
FIG. 8 is a graph of defect state density for the control and PSCs after 2D-PVK co-passivation.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
SnO2The preparation method of the electron transport layer comprises the following steps: 27.08mg of SnCl2 2H2O, dissolved in 3156mg of absolute ethanol. Sealing with a sealing film, wrapping with tinfoil, and standing in dark for 24 hours for later use. Before use, the mixture is filtered by a filter head with the diameter of 0.2 mu m.
The preparation method of the perovskite precursor liquid comprises the following steps: 8.5mg of FPEAI, 81mg of FAI and 223mg of PbI2Dissolving the mixture in a mixed solution of 50 mu L NMP and 300mg DMF, sealing the mixture with a sealing film, and strongly stirring the mixture for 5 to 10 minutes by using an electric stirrer.
Preparing a P VK solution: dissolving 10mg of PVK in 10ml of CB solvent, heating and stirring the solution on a hot plate at 80 ℃ for a night, naturally cooling the solution and storing the solution for later use, wherein the solution is sealed by a sealing film and protected from light during storage, and the solution is diluted by CB according to the concentration planned by an experiment before use according to the required proportion.
Preparation method of hole transport layer Spiro-OMeTAD solution: 72.3mg of the hole transport material, Spiro-OMeTAD, was added to 1mL of chlorobenzene solution, followed by 28.8. mu.L of 4-tert-butylpyridine and 17.5. mu.L of lithium bistrifluoromethanesulfonylimide solution.
Example 2:
the embodiment discloses a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundaries and surface defects, which comprises the following preparation steps:
the substrate is made of ITO with electric conduction grown on glass. SnO prepared by example 12Solution, perovskite precursor solution, PVK solution and Spiro-OMeTAD solution.
(1) By first cleaning the substrate, 15X 15mm, before preparing the electron transport layer2Square glass with one side coated with 7.5X 15mm2ITO of (2). Respectively using detergent, deionized water, ethanol and isopropyl alcoholUltrasonic cleaning with alcohol for 30 min. N for washed substrate2Blowing by an air gun, placing into a watch glass, treating for 12min by using ultraviolet-ozone cleaning equipment, and storing in a dust-free environment for later use.
(2) SnO preparation method adopting single-step spin coating process2An electron transport layer. Starting the spin coater, setting 3000 turns for 30s, placing the ITO substrate after ozone treatment on a rotary bracket of the spin coater, fixing the ITO substrate by vacuum adsorption, and taking 30 mu L SnO2Uniformly coating the sol-gel solution on a substrate, starting a spin coater, moving the sample to a hot plate at 150 ℃ after the spin coater stops rotating, annealing for 30min, moving the sample to a metal heat conducting plate after annealing, and cooling to room temperature. In order to improve SnO2The coverage of the film, the same spin coating process was repeated once more and annealed for 5 minutes, then 120 minutes, and after annealing, the hot plate was turned off and naturally cooled to room temperature.
(3) Growing FAPBI3The perovskite light absorption layer is prepared by adopting a one-step spin coating method; taking 25 mu L of FAPBI with 2D material3The uniform precursor solution of the perovskite precursor solution is uniformly coated on the SnO treated by ozone2Starting a spin coater on the ITO sample, wherein the spin coating setting is 4000 turns for 30 s; when the distance is about 15-17 s, 180 mu L of the anti-solvent (CB solution doped with PVK) is dripped. After the spin coater stops rotating, the sample is moved to a hot plate at 150 ℃ for annealing for 20 minutes, and then is moved to a metal heat conducting plate to be cooled to room temperature after annealing.
(4) Preparing a hole transport layer Spiro-OMeTAD by adopting a single-step dynamic spin coating method, namely setting a spin coater to rotate for 25s, placing a prepared semi-finished product, starting the spin coater, dropping 14uL of prepared Spiro-OMeTAD solution on a rotating sample at a constant speed within 15-18 s from the end of rotation, and stopping the spin coater to obtain the sample for steaming an electrode.
(6) And (4) evaporating the gold electrode by adopting a thermal evaporation method. And putting a sample of the hole transport layer Spiro-OMeTAD in a designed metal mold, and evaporating metal Au on the surface layer (with the thickness of about 60nm) of the hole transport layer Spiro-OMeTAD by using a vacuum coating instrument to obtain the perovskite solar cell device with a complete structure.
For PVK-2D perovskitt grown under the above conditionse/SnO2the/ITO (see the structural formula 1) perovskite thin film surface TEM (see figure 2), XRD, TRPL (see figure 3) and the like tests to determine the synergistic passivation effect of 2D-PVK on the perovskite thin film grain boundary and surface defects.
Example 3:
the embodiment discloses a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundaries and surface defects, which comprises the following preparation steps:
the substrate is made of ITO with electric conduction grown on glass. SnO prepared by example 12Solution, perovskite precursor solution, PVA solution and Spiro-OMeTAD solution.
(1) By first cleaning the substrate, 15X 15mm, before preparing the electron transport layer2Square glass with one side coated with 7.5X 15mm2ITO of (2). Ultrasonic cleaning with detergent, deionized water, ethanol and isopropanol for 30 min. N for washed substrate2Blowing by an air gun, placing into a watch glass, treating for 12min by using ultraviolet-ozone cleaning equipment, and storing in a dust-free environment for later use.
(2) SnO preparation method adopting single-step spin coating process2An electron transport layer. Starting the spin coater, setting 3000 turns for 30s, placing the ITO substrate after ozone treatment on a rotary bracket of the spin coater, fixing the ITO substrate by vacuum adsorption, and taking 30 mu L SnO2Uniformly coating the sol-gel solution on a substrate, starting a spin coater, moving the sample to a hot plate at 150 ℃ after the spin coater stops rotating, annealing for 30min, moving the sample to a metal heat conducting plate after annealing, and cooling to room temperature. In order to improve SnO2The coverage of the film, the same spin coating process was repeated once more and annealed for 5 minutes, then 120 minutes, and after annealing, the hot plate was turned off and naturally cooled to room temperature.
(3) Growing FAPBI3The perovskite light absorption layer is prepared by adopting a one-step spin coating method; taking 25 mu L of FAPBI with 2D material3The uniform precursor solution of the perovskite precursor solution is uniformly coated on the SnO treated by ozone2Starting a spin coater on the ITO sample, wherein the spin coating setting is 4000 turns for 30 s; when the distance is about 15-17 s, 180 mu L of the anti-solvent (CB solution doped with PVK) is dripped. After the spin coater stops rotating, the spin coater willThe sample is moved to a hot plate at 150 ℃ for annealing for 20 minutes, and then is moved to a metal heat conducting plate to be cooled to room temperature after annealing.
(4) Preparing a hole transport layer Spiro-OMeTAD by adopting a single-step dynamic spin coating method, namely setting a spin coater to rotate for 25s, placing a prepared semi-finished product, starting the spin coater, dropping 14uL of prepared Spiro-OMeTAD solution on a rotating sample at a constant speed within 15-18 s from the end of rotation, and stopping the spin coater to obtain the sample for steaming an electrode.
(6) And (4) evaporating the gold electrode by adopting a thermal evaporation method. And putting a sample of the hole transport layer Spiro-OMeTAD in a designed metal mold, and evaporating metal Au on the surface layer (with the thickness of about 60nm) of the hole transport layer Spiro-OMeTAD by using a vacuum coating instrument to obtain the perovskite solar cell device with a complete structure.
For Au/Spiro-OMeTAD/PVK-2D perovskite/SnO grown under the conditions2the/ITO device is subjected to a current-voltage (J-V) test (see FIG. 4), a stable output test (see FIG. 5), a transient photovoltage decay curve (see FIG. 6), an operation stability under illumination test (see FIG. 7) and a trap state density test (see FIG. 8). Test results show that after 2D-PVK synergistic passivation, the efficiency and the working stability of the device are greatly increased); the defect state density is significantly reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. A solar cell device based on 2D-PVK cooperative co-passivation of perovskite thin film grain boundaries and surface defects is characterized by comprising a conductive substrate, an electron transport layer, an organic-inorganic hybrid metal halide perovskite light absorption layer and a cooperative passivation layer which are sequentially preparedA layer of oxide, a hole transport layer and a metal electrode layer; the conductive substrate is indium tin oxide conductive glass; the electron transport layer is SnO2Sol-gel with a thickness of 25-35 nm; the light absorption layer of the organic-inorganic hybrid metal halide perovskite is FAPbI3Perovskite thin film layer, FAPbI3The 2D material is present at the grain boundaries of the perovskite thin film layer and is present at FAPBI3The surface of the perovskite thin film layer is provided with a PVK thin layer, FAPBI3The thickness of the perovskite thin film layer is 400-600 nm, and the thickness of the PVK thin film layer is 3-5 nm; the hole transport layer is a solid electrolyte Spiro-OMeTAD layer, and the thickness of the hole transport layer is 150-200 nm; the photo-anode is a metal thin film layer, and the thickness of the photo-anode is 50-70 nm.
2. A preparation method of a solar cell device based on 2D-PVK synergistic co-passivation of perovskite thin film grain boundaries and surface defects is characterized by comprising the following steps: an electron transport layer, an organic-inorganic hybrid metal halide perovskite light absorption layer and a hole transport layer are sequentially grown on a conductive substrate by adopting an all-solution method, and a gold electrode is evaporated on the hole transport layer to prepare the solar cell device based on 2D-PVK synergistic co-passivation perovskite thin film grain boundary and surface defects;
the preparation method of the electron transport layer comprises the following steps: SnCl2·2H2O and absolute ethyl alcohol are mixed according to a mass ratio of 1: 116-118, sealing with a sealing film, wrapping with tinfoil to prevent light, standing at room temperature for 24 hours to obtain transparent and uniform SnO2Sol-gel, which is filtered by a filter head with the diameter of 0.2 μm before use; preparing by adopting a single-step spin coating method, starting a spin coater, setting 3000 revolutions for 30s, placing the conductive substrate after ozone treatment on a rotary bracket of the spin coater, fixing the conductive substrate by vacuum adsorption, and carrying out SnO treatment2Dropping the sol-gel in the center of the conductive substrate, starting a spin coater, moving the sample to a hot plate at 145-155 ℃ after the spin coater stops rotating, annealing for 25-35 min, moving the sample to a metal heat conducting plate after annealing, and cooling to room temperature to obtain SnO2An ITO sample; wherein, 45 μ L of SnO2The sol-gel has an area of 1.5 × 1.5cm corresponding to the conductive substrate2；
Organic-inorganicThe preparation method of the organic hybrid metal halide perovskite light absorption layer comprises the following steps: and (2) mixing the following components in percentage by mass: 810: 223 FPEAI, HC (NH)2)2I and PbI2Dissolving the precursor solution in a mixed solution of N-methyl-2-propiophenone and N, N-dimethylformamide with the volume mass ratio of 65 mu L to 3000mg, sealing the solution with a sealing film, and stirring the solution for 5 to 10 minutes by using an electric stirrer to obtain a precursor solution of the perovskite precursor solution; dissolving PVK in chlorobenzene to obtain a chlorobenzene solution of PVK with the concentration of 1mg/mL, stirring for more than 10 hours at room temperature, and standing for 12 hours at room temperature to obtain a transparent and uniform perovskite precursor solution; the preparation method is characterized in that a one-step spin coating method is adopted, and the perovskite precursor solution is uniformly coated on SnO treated by ozone for 15-25 min2On an ITO sample, setting a spin coater to rotate for 30s at 4000 times; dripping the PVK chlorobenzene solution on the rotating SnO at a stable and uniform speed within 15-17 s from the end of rotation2On an ITO sample, after the spin coater stops rotating, the sample is moved to a hot plate at 145-155 ℃, annealing is carried out for 20-25 min, and after annealing, the sample is moved to a metal heat conducting plate and cooled to room temperature to obtain PVK-2D perovskite/SnO2An ITO sample; wherein, the area relation between the chlorobenzene solution of PVK and the conductive substrate is as follows: 180-200 μ L for 1.5X 1.5cm2A conductive substrate;
the preparation method of the hole transport layer comprises the following steps: the mass-to-volume ratio of the hole transport material Spiro-OMeTAD to the chlorobenzene solution is 343 mg: 4mL of the solution is mixed, and then 4-tert-butylpyridine and a lithium bistrifluoromethanesulfonylimide solution are sequentially added; chlorobenzene solution: 4-tert-butylpyridine: the volume ratio of the lithium bistrifluoromethanesulfonylimide solution is 4000: 135: 77; the preparation method adopts a single-step spin coating method, a spin coating machine is started, 3000 revolutions are set for 30s, and PVK-2D perovskite/SnO is put2The ITO sample is placed on a rotary bracket of a spin coater and fixed through vacuum adsorption, the spin coater is started, and the Spiro-OMeTAD solution is stably dripped on the rotating PVK-2D perovskite/SnO at a constant speed within 18-20 s from the end of rotation2Stopping rotating the spin coater on the ITO sample to obtain a hole transport layer; wherein, the relationship between the area of the Spiro-OMeTAD solution and the area of the conductive substrate is as follows: 15 μ L for 1.5X 1.5cm2A conductive substrate;
finally, the gold electrode is evaporated to obtain the structure Au/Spiro-OMeTAD/PVK-2Dperovskite/SnO2ITO based organic-inorganic hybrid metal halide perovskite solar cell device based on PVA passivation film surface/interface defects, namely the solar cell device based on 2D-PVK synergistic co-passivation perovskite film grain boundary and surface defects.
3. A production method according to claim 2, wherein in the production of the electron transport layer, SnO is enhanced2And (3) repeating the same spin coating process once again, firstly moving the sample to a hot plate at 145-155 ℃ for annealing for 5-7 min, cooling to room temperature, and then annealing on the hot plate at 145-155 ℃ for 110-130 min.
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