CN106960908B - Cathode modified planar perovskite solar cell and preparation method thereof - Google Patents

Cathode modified planar perovskite solar cell and preparation method thereof Download PDF

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CN106960908B
CN106960908B CN201710176355.XA CN201710176355A CN106960908B CN 106960908 B CN106960908 B CN 106960908B CN 201710176355 A CN201710176355 A CN 201710176355A CN 106960908 B CN106960908 B CN 106960908B
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高进伟
张文辉
丁阳
姜月
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South China Normal University
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Abstract

The invention discloses a cathode modified planar perovskite solar cell and a preparation method thereof, wherein the cathode modified planar perovskite solar cell sequentially comprises a conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer, a cathode modification layer and a metal counter electrode from bottom to top, the cathode modification layer is made of acetylacetone Titanium Oxide (TOPD), the cathode modification layer is arranged to reduce a contact potential barrier between the cathode metal electrode and the electron transport layer to a certain extent, so that the series resistance is reduced, the filling factor and the current density are improved to a great extent, and the energy conversion efficiency is effectively improved; on the other hand, compared with the method of utilizing thermal evaporation to deposit the inorganic cathode interface modification layer, the preparation process is greatly simplified, and the preparation cost is reduced. The whole process of the invention adopts a low-temperature preparation process, and provides a new approach and reliability for realizing the commercialization of the high-efficiency flexible perovskite solar cell.

Description

Cathode modified planar perovskite solar cell and preparation method thereof
Technical Field
The invention belongs to the field of planar perovskite solar cells, and particularly relates to an alcoholic solution cathode interface modified planar perovskite solar cell and a preparation method thereof.
Background
With the increasing exhaustion of fossil fuels, the development of clean energy is a necessary means for the sustainable development of human beings. Solar cells provide inexhaustible clean energy by converting continuous solar energy into electric energy, and are an important strategy for seeking sustainable development.
At present, the commercialized cell is mainly dominated by a silicon solar cell and a compound solar cell thereof, the material cost and the preparation cost are higher, and the development of the cell is restricted because of the higher costThe novel solar cell with low cost and simple preparation process becomes the focus of competitive research of various countries. Particularly, the perovskite solar cell has low cost and simple preparation process, in 2009, Miyasaka et al in Japan quotes the organic-inorganic mixed perovskite material MAPbI for the first time3And MAPbBr3The dye sensitizer is used for fuel sensitized solar cells, and the performance of the device is greatly improved. Such organic-inorganic hybrid perovskite materials have received much attention since then. In short years, the perovskite solar cell technology is developed rapidly, the efficiency is increased rapidly from 3.8% to 22%, the efficiency far exceeds that of an organic solar cell (OPV), a dye-sensitized solar cell (DSSC) and a quantum dot solar cell, the level of the existing mature CuInGaSe thin-film solar cell is reached, however, the cost of core materials is greatly low, the operation process is very simple, and the perovskite thin-film solar cell becomes one of the most potential stars in a third-generation novel thin-film solar cell.
At present, two types of perovskite solar cells are mainly used, one type is an n-i-p type perovskite solar cell based on an inorganic semiconductor oxide as a photoanode, the preparation process of the cell structure usually needs a high-temperature annealing process, the other type is a p-i-n type perovskite solar cell based on a polymer semiconductor hole transport layer as the photoanode, the structure and the preparation process are simple, the preparation can be carried out at a low temperature, a road is opened for the development of flexible solar cells, and the performance of the device is relatively reduced. In order to improve the performance of the p-i-n line reverse plane perovskite solar cell, the invention adopts an alcoholic solution cathode interface modification with low cost and simple process, reduces the contact potential barrier between the cathode and the electron transmission layer to a certain extent, reduces the series resistance, improves the filling factor and the current density to a great extent, and effectively improves the energy conversion efficiency.
Disclosure of Invention
The invention aims to provide a cathode modified planar perovskite solar cell, which effectively improves the energy conversion efficiency.
Another object of the present invention is to provide a method for manufacturing the above solar cell.
The aim of the invention is achieved by the following technical measures: the utility model provides a negative pole modification type plane perovskite solar cell, includes electrically conductive substrate, hole transport layer, perovskite layer, electron transport layer and metal counter electrode from bottom to top in proper order, its characterized in that: and a cathode interface modification layer is arranged between the electron transmission layer and the metal counter electrode, and is made of acetylacetone Titanium Oxide (TOPD).
The other purpose of the invention is realized by the following technical measures: a preparation method of a cathode modified type planar perovskite solar cell comprises the following steps:
(1) selecting a conductive substrate and etching the pattern, and cleaning to obtain an etched conductive base;
(2) performing plasma treatment on the etched conductive substrate in the step (1), depositing a polymer semiconductor hole transport material by using a spin coating method, and annealing to obtain a hole transport layer;
(3) preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on the hole transport layer in the step (2), adding an anti-solvent in the spin-coating process, annealing after spin-coating, and cooling to obtain a compact perovskite thin film;
(4) spin-coating a fullerene derivative electron transport layer solution on the compact perovskite thin film obtained in the step (3) to obtain an electron transport layer;
the method is characterized in that: also comprises
(5) Preparing an interface modification layer solution, and spin-coating the cathode interface modification layer solution on the electron transport layer obtained in the step (4) to obtain an interface modification layer;
the interface modification layer is made of titanium oxide acetylacetonate (TOPD) which is prepared into isopropanol solution of titanium oxide acetylacetonate with the solution of 2-5 mg/ml;
the spin coating speed of the spin coating cathode interface modification layer is 2000-5000 rpm/min, the spin coating time is 20-40 s, the annealing temperature is 60-100 ℃, the annealing time is 10-15 min, and the obtained thickness is 5-15 nm;
(6) and (5) performing thermal evaporation on the cathode interface modification layer obtained in the step (5) to obtain a gold or silver electrode, so as to obtain the high-efficiency p-i-n type planar perovskite solar cell.
Preferably, the invention is configured to have a solution of 3mg/ml of titanium oxide acetylacetonate in isopropanol; the spin coating speed of the spin coating cathode interface modification layer is 3000rpm/min, the spin coating time is 30s, the annealing temperature is 60 ℃, the annealing time is 15min, and the thickness is 10 nm.
The conductive substrate in step (1) of the present invention is preferably FTO glass, ITO glass or ITO/PET substrate.
The process of cleaning the conductive substrate in the step (1) comprises the step of ultrasonic cleaning for 10-20 min by using a detergent aqueous solution, deionized water, acetone and isopropanol respectively.
The plasma treatment time in the step (2) is 10-20 min, the hole transport layer is made of PEDOT (Poly ethylene styrene) PSS (Poly ethylene styrene) or Poly-TPD (Poly ethylene styrene), the spin coating speed of the spin coating of the hole transport layer is 2000-5000 rpm/min, the spin coating time is 20-40 s, the annealing temperature is 120-150 ℃, the annealing time is 10-15 min, and the thickness of the obtained hole transport layer is 20-50 nm.
In the step (3), the perovskite solution is a mixed solution of lead iodide and methyl amine iodide, wherein the quantity relation of substances of the lead iodide and the methyl amine iodide is 1: 0.8-1.15, the solvent of the mixed solution is a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 6-9: 1-4.
The spin coating speed of the spin coating perovskite solution in the step (3) is 3000-5000 rpm/min, the spin coating time is 20-30 s, the anti-solvent is dripped at the 6 th-10 th time, the annealing temperature is 100-105 ℃, the annealing time is 10-20 min, and the thickness of the obtained perovskite thin film is 300-500 nm.
The fullerene derivative electron transport layer solution in the step (4) is a chlorobenzene solution of fullerene derivative PCBM, and the concentration of the chlorobenzene solution is 10-30 mg/mL; when the fullerene derivative electron transport layer solution is spin-coated, the spin-coating speed is 1000-3000 rpm/min, the spin-coating time is 20-40 s, and the spin-coating thickness is 20-60 nm.
When the gold or silver electrode is plated in hot gold or silver in the step (6), the evaporation rate is distributed in a step mode, and the distribution rule is as follows: evaporating at the rate of 0.1-0.3A/s for 3-8 min, evaporating at the rate of 0.5-0.8A/s for 7-12 min, and evaporating at the rate of 1-1.2A/s for 8-15 min to obtain a gold or silver electrode with the thickness of 50-120 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional inverted junction plane perovskite solar cell, the method provided by the invention has the main process difference that a cathode modification layer of acetylacetone titanium oxide is introduced between the electron transmission layer and the cathode metal electrode, so that the contact potential barrier between the cathode metal electrode and the electron transmission layer is reduced to a certain extent, the series resistance is reduced, the filling factor and the current density are improved to a great extent, the energy conversion efficiency reaches 13.48%, the short-circuit current density reaches 20.7, the filling factor reaches 76.35%, and the open-circuit voltage reaches 0.85V.
(2) The method adopts the acetylacetone titanium oxide alcoholic solution as interface modification, greatly simplifies the preparation process and reduces the preparation cost compared with the method of utilizing a thermal evaporation inorganic cathode interface modification layer, and provides a new approach and reliability for preparing the high-efficiency low-temperature planar flexible perovskite solar cell;
drawings
FIG. 1 is a flow chart of the preparation of an alcoholic solution cathode modified reverse planar perovskite solar cell in an embodiment of the invention;
FIG. 2 is a current density-voltage graph of an alcoholic solution cathode modified reverse planar perovskite solar cell prepared in example 1 of the present invention;
FIG. 3 is a current density-voltage plot of a non-cathode modified reverse planar perovskite solar cell prepared in accordance with example 1 of the present invention as compared to a conventional method;
FIG. 4 is a graph of current density versus voltage comparing alcoholic solution cathode modified reverse planar perovskite solar cells prepared in accordance with the present invention (example 1) with conventional reverse planar perovskite solar cells (example 2);
FIG. 5 is a current density-voltage graph of an alcoholic solution cathode modified reverse planar perovskite solar cell prepared in example 2 of the present invention;
FIG. 6 is a current density-voltage graph of an alcoholic solution cathode modified reverse planar perovskite solar cell prepared in example 3 of the present invention;
FIG. 7 is a graph of current density versus voltage for an alcoholic solution cathode modified reverse planar perovskite solar cell prepared in accordance with the present invention as a function of scan direction;
FIG. 8 is a graph of current density versus voltage for an alcoholic solution cathode modified reverse planar perovskite solar cell prepared in accordance with the present invention as a function of scan rate;
wherein in FIG. 1:1 is a conductive substrate, 2 is a hole transport layer, 3 is a perovskite thin film, 4 is an electron transport layer, 5 is an acetylacetone titanium oxide cathode modification layer, and 6 is a metal Ag counter electrode
Detailed Description
Example 1
As shown in fig. 1, the method for preparing a high-efficiency non-inhibition planar perovskite solar cell by modifying an alcoholic solution cathode interface sequentially includes the following steps:
(1) etching ITO transparent conductive glass into a required target pattern by laser, then sequentially ultrasonically cleaning the etched conductive substrate by using a conventional detergent aqueous solution, deionized water, acetone and isopropanol for 20 minutes, and then drying the substrate by blowing by using nitrogen to obtain a clean conductive substrate for later use;
(2) treating the surface with plasma (by a conventional plasma cleaner) for 10 minutes before use to perform hydrophilization treatment, spin-coating a polymer semiconductor hole transport material (poly-3, 4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT: PSS) (model: PEDOT AL4083) on a conductive substrate at the spin-coating speed of 3000rpm/min for 30s, and annealing on a hot table at 120 ℃ for 15 minutes to obtain a hole transport layer with the thickness of about 30 nm;
(3) cooling, spin-coating perovskite precursor solution (PbI) with concentration of 1.25mol/L2): methyl amine iodide (CH)3NH3I) Dissolving in mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) at volume ratio of 7:3, stirring at 70 deg.C for 12 hr, and performing two-step spin coating at first speed of 500rpm for 5s and second speed of 5000rpm, spin-coating for 25s, dropwise adding 1mL of anhydrous toluene in the 10 th s of the second-step high-speed spin coating, and then annealing the spin-coated film at 100 ℃ for 10 minutes to obtain a compact perovskite film, wherein the thickness of the obtained perovskite film is 400 nm;
(4) spin-coating the electron transport layer material, wherein the electron transport layer solution is chlorobenzene solution of fullerene derivative (PCBM), the concentration of the electron transport layer solution is 20mg/mL, the spin-coating speed is 1000rpm/min, and the spin-coating time is 20s, so that the electron transport layer with the thickness of 50nm is obtained.
(5) Spin-coating a cathode interface modification layer material, wherein the cathode interface modification layer solution is an isopropanol solution of acetylacetone Titanium Oxide (TOPD), the concentration of the isopropanol solution is 3mg/mL, the spin-coating speed is 3000rpm/min, the spin-coating time is 30min, and annealing is carried out at 60 ℃ for 15min, so that a cathode interface modification layer with the thickness of 10nm is obtained.
(6) And finally, evaporating an Ag electrode, wherein the evaporation rate is distributed in a step mode when the silver electrode is hot-dipped, and the distribution rule is that evaporation is carried out for 5min at the rate of 0.2A/s, 8min at the rate of 0.6A/s and 12min at the rate of 1A/s, so that the silver electrode with the thickness of about 120nm is obtained.
The cathode modified planar perovskite solar cell prepared by the method sequentially comprises an ITO substrate, a hole transport layer, a perovskite layer, an electron transport layer, a cathode interface modification layer and a metal counter electrode from bottom to top. The I-V test result of the prepared planar perovskite solar cell is shown in figure 2, the energy conversion efficiency is up to 13.48%, the short-circuit current density is up to 20.7mA/cm2, the filling factor is up to 76.35%, the open-circuit voltage is up to 0.85V, and the prepared planar perovskite solar cell has higher current density and filling factor due to the cathode interface modification of the invention.
A comparative test was conducted on the above example 1, and a reverse planar perovskite solar cell was prepared by a conventional method, specifically as follows:
(1) etching ITO transparent conductive glass into a required target pattern by laser, then sequentially ultrasonically cleaning the etched conductive substrate by using a conventional detergent aqueous solution, deionized water, acetone and isopropanol for 20 minutes, and then drying the substrate by blowing by using nitrogen to obtain a clean conductive substrate for later use;
(2) treating the surface with plasma (conventional plasma cleaner) for 10 min before use to perform hydrophilization treatment, spin-coating a polymer semiconductor hole transport material (poly-3, 4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT: PSS) (model: PEDOT AL4083) on a conductive substrate at the spin-coating speed of 3000rpm/min for 30s, and annealing on a hot table at 120 ℃ for 15min to obtain a hole transport layer with the thickness of 30 nm;
(3) cooling, spin-coating perovskite precursor solution (PbI) with concentration of 1.25mol/L2): methyl amine iodide (CH)3NH3I) Dissolving the perovskite thin film in a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 7:3 (1: 1), stirring at 70 ℃ for 12 hours, performing two-step spin coating, adjusting the spin coating speed to be 500rpm and 5s in the first step, adjusting the rotation speed to be 5000rpm in the second step, performing spin coating for 25s, dropwise adding 1mL of anhydrous toluene into the 10 th s of the high-speed spin coating in the second step, and annealing the spin-coated thin film at 100 ℃ for 10 minutes to obtain a compact perovskite thin film, wherein the thickness of the obtained perovskite thin film is 400 nm;
(4) spin-coating the electron transport layer material, wherein the electron transport layer solution is chlorobenzene solution of fullerene derivative (PCBM), the concentration of the electron transport layer solution is 20mg/mL, the spin-coating speed is 1000rpm/min, and the spin-coating time is 20s, so that the electron transport layer with the thickness of 50nm is obtained.
(5) And finally, evaporating an Ag electrode, wherein the evaporation rate is distributed in a step mode when the silver electrode is hot-dipped, and the distribution rule is that evaporation is carried out for 5min at the rate of 0.2A/s, 8min at the rate of 0.6A/s and 12min at the rate of 1A/s, so that the silver electrode with the thickness of about 120nm is obtained. The prepared product is not provided with a cathode interface modification layer, and the I-V test result of the product is shown in figure 3, so that the energy conversion efficiency is up to 7.67%, the short-circuit current density is up to 13.93mA/cm2, the filling factor is 69.54%, and the open-circuit voltage is 0.80V.
In the first embodiment of the present invention, compared with the current density-voltage curve of the conventional reverse planar perovskite solar cell, as shown in fig. 4, by comparing the I-V characteristic curves of the first embodiment and the conventional method, the current density of the cell prepared by cathode interface modification is 20.7mA/cm2 and the fill factor is 76.35%, which are greatly improved compared with the current densities of 13.93mA/cm2 and 69.54% of the conventional planar perovskite solar cell, which indicates that the interface resistance between the electron transport layer and the electrode can be reduced by the cathode interface layer, and the recombination of carriers can be reduced.
Example 2
As shown in fig. 1, the method for preparing a high-efficiency non-inhibition planar perovskite solar cell by alcoholic solution cathode interface modification in the embodiment includes the following steps:
(1) etching FTO transparent conductive glass into a required target pattern by laser, then sequentially ultrasonically cleaning the etched conductive substrate by using a conventional detergent aqueous solution, deionized water, acetone and isopropanol for 20 minutes, and then drying the substrate by using nitrogen to obtain a clean conductive substrate for later use;
(2) treating the surface with plasma (by a conventional plasma cleaner) for 10 minutes before use to perform hydrophilization treatment, spin-coating a polymer semiconductor hole transport material (poly-3, 4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT: PSS) (model: PEDOT AL4083) on a conductive substrate at the spin-coating speed of 3000rpm/min for 30s, and annealing on a hot table at 120 ℃ for 15 minutes to obtain a hole transport layer with the thickness of about 30 nm;
(3) cooling, spin-coating perovskite precursor solution (PbI) with concentration of 1.25mol/L2): methyl amine iodide (CH)3NH3I) Dissolving the perovskite thin film in a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 7:3 (1: 1), stirring at 70 ℃ for 12 hours, performing two-step spin coating, adjusting the spin coating speed to be 500rpm and 5s in the first step, adjusting the rotation speed to be 5000rpm in the second step, performing spin coating for 25s, dropwise adding 1mL of anhydrous toluene into the 10 th s of the high-speed spin coating in the second step, and annealing the spin-coated thin film at 100 ℃ for 10 minutes to obtain a compact perovskite thin film, wherein the thickness of the obtained perovskite thin film is 400 nm;
(4) spin-coating the electron transport layer material, wherein the electron transport layer solution is chlorobenzene solution of fullerene derivative (PCBM), the concentration of the electron transport layer solution is 20mg/mL, the spin-coating speed is 1000rpm/min, and the spin-coating time is 20s, so that the electron transport layer with the thickness of 50nm is obtained.
(5) Spin-coating a cathode interface modification layer material, wherein the cathode interface modification layer solution is an isopropanol solution of acetylacetone Titanium Oxide (TOPD), the concentration of the isopropanol solution is 2mg/mL, the spin-coating speed is 4000rpm/min, the spin-coating time is 40min, and annealing is carried out at 60 ℃ for 15min, so that a cathode interface modification layer with the thickness of 5nm is obtained.
(6) And finally, evaporating an Ag electrode, wherein the evaporation rate is distributed in a step mode when the silver electrode is hot-dipped, and the distribution rule is that evaporation is carried out for 5min at the rate of 0.2A/s, 8min at the rate of 0.6A/s and 12min at the rate of 1A/s, so that the silver electrode with the thickness of about 120nm is obtained.
The results of the I-V test of this example 2, as shown in FIG. 5, resulted in an energy conversion efficiency as high as 9.12%, a short circuit current density as high as 15.02mA/cm2, a fill factor as high as 75.56%, and an open circuit voltage as high as 0.80V, which were improved relative to the conventional method, but the current density was slightly reduced relative to the first example, from 20.7 to 15.02, and the fill factor was slightly reduced relative to comparative examples 1 and 2, because the thickness of the TOPD cathode finish formed in example 2 was reduced from 10nm to 5nm, resulting in a reduction in current density and thus efficiency.
Example 3
As shown in fig. 1, the method for preparing a high-efficiency non-inhibition planar perovskite solar cell by alcoholic solution cathode interface modification in the embodiment includes the following steps:
(1) etching ITO transparent conductive glass into a required target pattern by laser, then sequentially ultrasonically cleaning the etched conductive substrate by using a conventional detergent aqueous solution, deionized water, acetone and isopropanol for 20 minutes, and then drying the substrate by blowing by using nitrogen to obtain a clean conductive substrate for later use;
(2) treating the surface with plasma (by a conventional plasma cleaner) for 10 minutes before use to perform hydrophilization treatment, spin-coating a polymer semiconductor hole transport material (poly-3, 4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT: PSS) (model: PEDOT AL4083) on a conductive substrate at the spin-coating speed of 3000rpm/min for 30s, and annealing on a hot table at 120 ℃ for 15 minutes to obtain a hole transport layer with the thickness of about 30 nm;
(3) cooling and spin-coating perovskite precursor solution (iodine) with concentration of 1.25mol/LLead dissolving (PbI)2): methyl amine iodide (CH)3NH3I) Dissolving the perovskite thin film in a mixed solvent of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a volume ratio of 7:3 (1: 1), stirring at 70 ℃ for 12 hours, performing two-step spin coating, adjusting the spin coating speed to be 500rpm and 5s in the first step, adjusting the rotation speed to be 5000rpm in the second step, performing spin coating for 25s, dropwise adding 1mL of anhydrous toluene into the 10 th s of the high-speed spin coating in the second step, and annealing the spin-coated thin film at 100 ℃ for 10 minutes to obtain a compact perovskite thin film, wherein the thickness of the obtained perovskite thin film is 400 nm;
(4) spin-coating the electron transport layer material, wherein the electron transport layer solution is chlorobenzene solution of fullerene derivative (PCBM), the concentration of the electron transport layer solution is 20mg/mL, the spin-coating speed is 1000rpm/min, and the spin-coating time is 20s, so that the electron transport layer with the thickness of 50nm is obtained.
(5) Spin-coating a cathode interface modification layer material, wherein the cathode interface modification layer solution is an isopropanol solution of acetylacetone Titanium Oxide (TOPD), the concentration of the isopropanol solution is 5mg/mL, the spin-coating speed is 4000rpm/min, the spin-coating time is 30min, and annealing is carried out at 60 ℃ for 15min, so that a cathode interface modification layer with the thickness of 15nm is obtained.
(6) And finally, evaporating an Ag electrode, wherein the evaporation rate is distributed in a step mode when the silver electrode is hot-dipped, and the distribution rule is that evaporation is carried out for 5min at the rate of 0.2A/s, 8min at the rate of 0.6A/s and 12min at the rate of 1A/s, so that the silver electrode with the thickness of about 120nm is obtained.
The results of the I-V test of this example 3 are shown in FIG. 6, and the energy conversion efficiency is as high as 10.44%, the short circuit current density is as high as 17.13mA/cm2, the fill factor is as high as 75.15%, and the open circuit voltage is as high as 0.81V, which are greatly improved compared with the conventional method, but the current density is slightly reduced from 20.7 to 17.13 compared with the example one, and the fill factor is slightly reduced compared with the comparative examples 1 and 3, because the thickness of the TOPD cathode modified layer formed by the example 3 is increased from 10nm to 15nm, which results in a reduction in the current density and a reduction in the efficiency.
In order to verify the inhibition effect of the alcoholic solution cathode modified perovskite solar cell prepared by the invention, the product prepared in the example 3 is tested, the current density-voltage curve graph of the prepared cell changes along with the scanning direction, as shown in the I-V test results when the scanning speed is respectively 1.4V/s, 1.12V/s, 0.7V/s, 0.42V/s and 0.14V/s in the change of the current density-voltage curve graph and the scanning speed are shown in figure 7 and figure 8, the I-V curve hardly changes obviously under the conditions of forward scanning and reverse scanning, and the I-V curves are almost overlapped under the conditions of different scanning speeds of 1.4V/s, 1.12V/s, 0.7V/s, 0.42V/s and 0.14V/s, which shows that the perovskite solar cell performance test prepared by the invention is not influenced by the scanning direction and the scanning speed, therefore, the perovskite solar cell prepared by the method has no inhibition effect. Other embodiments may also measure similar results, which are not described in detail.
Although the present invention has been described with reference to the above embodiments, it should be understood that the scope of the present invention is not limited thereto, and those skilled in the art can make modifications and alterations without departing from the spirit and scope of the present invention.

Claims (9)

1. The utility model provides a negative pole modification type plane perovskite solar cell, includes ITO substrate, hole transport layer, perovskite layer, electron transport layer and metal counter electrode from bottom to top in proper order, its characterized in that: a cathode interface modification layer is arranged between the electron transmission layer and the metal counter electrode, the cathode interface modification layer is obtained by spin-coating a cathode interface modification layer solution on the electron transmission layer, the cathode interface modification layer is made of acetylacetonato titanium oxide, and the prepared solution is 2-5 mg/ml isopropanol solution of acetylacetonato titanium oxide; the spin coating speed of the spin coating cathode interface modification layer is 2000-5000 rpm/min, the spin coating time is 20-40 s, the annealing temperature is 60-100 ℃, the annealing time is 10-15 min, and the thickness is 5-15 nm;
the perovskite layer is prepared by spin-coating a perovskite precursor solution on a hole transport layer, adding an anti-solvent in the spin-coating process, annealing after spin-coating, and cooling to obtain a compact perovskite thin film;
the perovskite precursor solution is a mixed solution of lead iodide and methyl amine iodide, wherein the quantity relation of the lead iodide and the methyl amine iodide is 1: 0.8-1.15, the solvent of the mixed solution is a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 6-9: 1-4.
2. A method for preparing the cathode modified planar perovskite solar cell of claim 1, comprising the steps of:
(1) selecting a conductive substrate and etching the pattern, and cleaning to obtain an etched conductive base;
(2) performing plasma treatment on the etched conductive substrate in the step (1), depositing a polymer semiconductor hole transport material by using a spin coating method, and annealing to obtain a hole transport layer;
(3) preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on the hole transport layer in the step (2), adding an anti-solvent in the spin-coating process, annealing after spin-coating, and cooling to obtain a compact perovskite thin film;
(4) spin-coating a fullerene derivative electron transport layer solution on the compact perovskite thin film obtained in the step (3) to obtain an electron transport layer;
the method is characterized in that: also comprises
(5) Preparing an interface modification layer solution, and spin-coating the cathode interface modification layer solution on the electron transport layer obtained in the step (4) to obtain an interface modification layer;
the interface modification layer material is acetylacetone titanium oxide, and the prepared solution is 2-5 mg/ml isopropanol solution of acetylacetone titanium oxide;
the spin coating speed of the spin coating cathode interface modification layer is 2000-5000 rpm/min, the spin coating time is 20-40 s, the annealing temperature is 60-100 ℃, the annealing time is 10-15 min, and the thickness is 5-15 nm;
(6) performing thermal evaporation on the cathode interface modification layer obtained in the step (5) to form a gold or silver electrode, so as to obtain a p-i-n type planar perovskite solar cell;
the perovskite precursor solution is a mixed solution of lead iodide and methyl amine iodide, wherein the quantity relation of the lead iodide and the methyl amine iodide is 1: 0.8-1.15, the solvent of the mixed solution is a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 6-9: 1-4.
3. The method of claim 2, wherein: preparing isopropanol solution of acetylacetone titanium oxide with the solution of 3mg/ml in the step (5); the spin coating speed of the spin coating cathode interface modification layer is 3000rpm/min, the spin coating time is 30s, the annealing temperature is 60 ℃, the annealing time is 15min, and the thickness is 10 nm.
4. The method of claim 2, wherein: the conductive substrate in the step (1) is FTO glass, ITO glass or ITO/PET substrate.
5. The method of claim 2, wherein: the process of cleaning the conductive substrate in the step (1) is to respectively use detergent aqueous solution, deionized water, acetone and isopropanol to carry out ultrasonic cleaning for 10-20 min.
6. The method of claim 2, wherein: the plasma treatment time in the step (2) is 10-20 min, and the hole transport layer is made of PEDOT: PSS or Poly-TPD, wherein the spin rate of the spin coating of the hole transport layer material is 2000-5000 rpm/min, the spin coating time is 20-40 s, the annealing temperature is 120-150 ℃, the annealing time is 10-15 min, and the thickness of the obtained hole transport layer is 20-50 nm.
7. The method of claim 2, wherein: and (3) the spin coating speed of the spin coating perovskite solution in the step (3) is 3000-5000 rpm/min, the spin coating time is 20-30 s, the anti-solvent is dripped at the 6 th-10 th time, the annealing temperature is 100-105 ℃, the annealing time is 10-20 min, and the thickness of the obtained perovskite thin film is 300-500 nm.
8. The method of claim 2, wherein: the fullerene derivative electron transport layer solution in the step (4) is a chlorobenzene solution of fullerene derivative PCBM, and the concentration of the chlorobenzene solution is 10-30 mg/mL; when the fullerene derivative electron transport layer solution is spin-coated, the spin-coating speed is 1000-3000 rpm/min, the spin-coating time is 20-40 s, and the spin-coating thickness is 20-50 nm.
9. The method of claim 2, wherein: when the hot gold or silver electrode is plated in the step (6), the evaporation rate is distributed in a step mode, and the distribution rule is as follows: evaporating at the rate of 0.1-0.3A/s for 3-8 min, evaporating at the rate of 0.5-0.8A/s for 7-12 min, and evaporating at the rate of 1-1.2A/s for 8-15 min to obtain a gold or silver electrode with the thickness of 50-120 nm.
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