CN115332455A - Perovskite solar cell regulated and controlled through crystallization and preparation method thereof - Google Patents

Abstract

The invention relates to a perovskite solar cell regulated through crystallization and a preparation method thereof, wherein the method comprises the following steps: drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment; preparing an electron conducting layer on the conductive base layer; preparing a prolinamide doped perovskite light absorbing layer on the electron conducting layer; preparing a proline modifying layer on the perovskite light absorption layer; preparing a hole conducting layer on the proline modifying layer; and sputtering a metal electrode on the hole conduction layer by using a magnetron sputtering instrument or an evaporation method to prepare a metal electrode layer. The contact between the electron conduction layer and the hole conduction layer can be effectively reduced, the leakage current is reduced, the photoelectric conversion efficiency is improved, the permeation of oxygen is blocked, and the stability of the perovskite material is improved.

Description

Perovskite solar cell regulated and controlled through crystallization and preparation method thereof

Technical Field

The invention belongs to the technical field of photovoltaic materials and devices, and particularly relates to a perovskite solar cell subjected to crystallization regulation and control and a preparation method thereof.

Background

In recent years, energy problems have been receiving much attention. Perovskite solar cells are widely studied as a new type of solar cell with its excellent photovoltaic performance and low manufacturing cost. However, the poor stability of the perovskite solar cell has been a serious problem hindering the industrialization of the perovskite solar cell. One of the key reasons affecting its optoelectronic properties and stability is the microscopic defects of its perovskite material.

A common perovskite solar cell structure includes, in order, an electrically conductive substrate, an electron conducting layer, a perovskite light absorbing layer, a hole conducting layer, and a metal electrode. The existing research shows that organic-inorganic hybrid perovskite material is used as a semiconductor material, free carriers are generated through a photoelectric effect under the condition of illumination, and after an external circuit is connected, free electrons and free holes move oppositely in the device through the energy level matching effect of each laminated material, so that voltage and current are generated. This is the working principle of perovskite solar cells.

For perovskite photovoltaic materials, microscopic defects such as grain boundaries, ion defects, dangling bonds and the like exist, and the defects can introduce defect deep energy levels to restrict normal transport of free carriers and cause adverse phenomena such as non-radiative recombination and the like, so that the overall performance of a solar cell is reduced. Passivation by using Lewis acid-base reaction (e.g., using some small molecular organic compounds) is a common defect passivation method. The additive and the precursor are subjected to addition reaction in the perovskite precursor, so that the reaction energy barrier is increased, the crystallization rate is slowed down, the crystallinity can be improved in the perovskite crystallization process, the generation of defects is reduced, and adverse effects caused by ion defects are neutralized.

Disclosure of Invention

The invention aims to provide a perovskite solar cell subjected to crystallization regulation and a preparation method thereof, so as to solve the problems in the background technology.

In order to realize the purpose, the technical scheme adopted by the invention is as follows:

a method of fabricating a crystallization-mediated perovskite solar cell, the method comprising:

(1) Drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment;

(2) Preparing an electron conducting layer on the conductive base layer;

(3) Preparing a prolinamide calcium doped perovskite light absorption layer on the electron conducting layer;

(4) Preparing a proline modifying layer on the perovskite light absorption layer;

(5) Preparing a hole conducting layer on the proline modifying layer;

(6) And sputtering a metal electrode on the hole conduction layer by using a magnetron sputtering instrument or an evaporation method to prepare a metal electrode layer.

As a further improvement of the invention, the step (1) comprises the following steps:

after the conductive substrate is subjected to partition treatment by laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing the conductive substrate by using deionized water and absolute ethyl alcohol, and sequentially and respectively ultrasonically cleaning the conductive substrate by using the substrate cleaning solution, the ethyl alcohol, the deionized water, the acetone and the ethyl alcohol for 15min after washing is finished to obtain a cleaned conductive base layer;

the substrate cleaning liquid is obtained by uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to the volume ratio of 30.

As a further improvement of the present invention, the step (2) includes:

taking 70 mu L of electronic conducting layer solution by using a liquid transfer gun at air environment and room temperature, spin-coating the solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the conductive substrate at a hot stage at 150 ℃ for 30 min after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electronic conducting layer;

the electronic conducting layer solution is obtained by uniformly mixing a tin dioxide nanocrystal solution and deionized water according to the proportion of 1.

As a further improvement of the present invention, the step (3) includes:

spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at a rotation speed of 1500 rpm with an acceleration of 800m/s, and annealing at 70 ℃ for 1 minute to form a lead iodide layer after the spin-coating;

after the surface is blown by nitrogen, 100-110 mu L of ammonium salt precursor solution is spin-coated on the lead iodide layer at the rotating speed of 1500-1700 rpm; heating the mixture in a nitrogen glove box at 70 ℃ for 50-60 seconds, then heating the mixture to 150 ℃ in an indoor air environment with the humidity of 45-60%, and preserving the heat for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

As a further improvement of the invention, the lead iodide precursor solution is obtained by mixing lead iodide and prolinamide according to a certain proportion, adding the mixture into a solvent of N, N-dimethylformamide and dimethyl sulfoxide mixed in a ratio of 9.

As a further improvement of the invention, the ammonium salt precursor solution is obtained by adding iodoformamidine, chloromethylamine and bromomethylamine in the mass ratio of (9-10): 2-1): 1 into an isopropanol solution, dissolving the mixture, and filtering the mixture by combining an injector and a filter tip.

As a further improvement of the invention, the step (4) comprises the following steps:

adding proline into a mixed solvent obtained by mixing ultrapure water, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 2;

40 μ L of the proline modifying layer solution was spin coated on the perovskite layer in a nitrogen glove box at 4000 rpm for 30 seconds, and then heat annealed at 75 ℃ for 1 minute to prepare the proline modifying layer.

As a further improvement of the invention, the step (5) comprises the following steps: and spin-coating 50 mu L of the hole conducting layer solution on the proline modification layer for 30 seconds in a nitrogen glove box at the rotating speed of 4000 rpm to prepare the hole conducting layer, and placing the hole conducting layer into a drying oven for oxidation for 24 hours after the spin-coating is finished.

As a further improvement of the present invention, the hole conducting layer solution is prepared as follows:

dissolving Li-TFSI by taking acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml;

dissolving Spiro-OMeTAD in chlorobenzene as a solvent, adding tBP and the Li-TFSI acetonitrile solution, and filtering by combining a syringe and a filter tip to obtain the product.

In another aspect, a perovskite solar cell is provided as prepared in the first aspect.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

according to the perovskite solar cell preparation method provided by the invention, prolinamide is used as a small molecular organic matter, has a condensation nucleus effect during perovskite crystallization, is used for improving the film forming property of a perovskite material, increasing perovskite crystal grains and reducing the loss of current carriers, amino groups and carbonyl groups of the prolinamide can form coordinate bonds and hydrogen bonds with various defects in perovskite so as to optimize a lattice structure distorted due to the defects, and Lewis basic functional groups (such as amino groups) can be combined with PbI type anti-site defects (lead ions replace iodide ions) and uncoordinated Pb (lead ions replace iodide ions) ²⁺ The defects are coordinated so as to counteract the constraint capacity of the defects on free carriers, and a plurality of dangling bonds formed by incompletely coordinated ions exist on the upper surface of the perovskite layer, and the dangling bonds serve as interface defects and have a strong barrier effect on the carrier transport. Adverse effects of dangling bonds on carrier transport can be weakened through coordination passivation of proline micromolecules in the proline modification layer. The photoelectric performance of the cell device is improved relative to an untreated perovskite solar cell device. After the perovskite solar cell is connected with an external circuit, the lattice structure enables the photogenerated carriers to flow into the external circuit under the action of the internal potential difference formed by the structure after the perovskite solar cell receives continuous illumination and exciton absorption occurs, and stable photogeneration is formedThe current is applied.

According to the perovskite solar cell prepared by the method, the perovskite light absorption layer thin film shows stronger crystallinity and a smoother surface after being doped with prolinamide, and dangling bonds on the surface of the perovskite layer between the interface of the perovskite light absorption layer and the interface of the hole conduction layer can be passivated by proline, so that the constraint of deep energy level defects on current carriers is reduced, the contact between an electron conduction layer and the hole conduction layer can be effectively reduced, the leakage current is reduced, the photoelectric conversion efficiency is improved, the oxygen permeation is favorably blocked, and the oxidation of perovskite materials is reduced.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

Fig. 1 is a schematic structural diagram of a perovskite solar cell subjected to crystallization regulation in example 1 according to the present invention.

Fig. 2 is a current density-voltage (J-V) curve test chart of the perovskite solar cells of examples 1, 2, 3 and comparative examples 1, 2.

Fig. 3 is a current density-voltage (J-V) curve test chart of the perovskite solar cells of examples 1, 4, 5 and comparative examples 1, 3.

Fig. 4 is a quantum efficiency test chart of the perovskite solar cell in example 1 and comparative example 1.

Fig. 5 is an Electrochemical Impedance (EIS) test chart of the perovskite solar cell according to example 1 and comparative example 1 of the present invention.

Fig. 6 is a test graph of Dark state current density-voltage (Dark J-V) curves of perovskite solar cells in example 1 according to the present invention and comparative example 1.

Fig. 7 is a Space Charge Limited Current (SCLC) test chart of a perovskite layer material in a perovskite solar cell according to comparative example 1 of the present invention.

Fig. 8 is a Space Charge Limited Current (SCLC) test chart of a perovskite layer material in a perovskite solar cell according to example 1 of the present invention.

Fig. 9 is an X-ray diffraction (XRD) pattern of the perovskite layer material of the perovskite solar cell in example 1 and comparative example 1 according to the present invention.

Fig. 10 is a uv-vis absorption spectrum of the perovskite layer material of the perovskite solar cell in example 1 and comparative example 1 according to the present invention.

Fig. 11 is an ultraviolet photoelectron spectrum of a perovskite layer material of the perovskite solar cell according to example 1 and comparative example 1 of the present invention.

Fig. 12 is a graph showing stability test of photoelectric conversion efficiency of the perovskite solar cell according to example 1 and comparative example 1 stored in a nitrogen glove box environment for 720 hours in a dark place.

Fig. 13 is a graph showing stability test of photoelectric conversion efficiency of the perovskite solar cell according to example 1 and comparative example 1 in one standard solar intensity for 240 hours of irradiation.

Fig. 14 is a graph showing stability test of photoelectric conversion efficiency of the perovskite solar cell according to example 1 and comparative example 1 stored for 720 hours in an air atmosphere with humidity of 40% to 60% at 3.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail and fully with reference to the following embodiments.

Example 1:

an embodiment of a method for preparing a perovskite solar cell through crystallization regulation comprises the following steps:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15%*15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and after washing is finished, sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol to obtain a cleaned conductive base layer;

1-4) drying the cleaned conductive substrate layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution and 2ml of deionized water by using a liquid transfer gun, uniformly mixing, and filtering by using a syringe and a filter tip combination to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electron conducting layer solution by using a liquid transfer gun under air environment and room temperature, spin-coating the electron conducting layer solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the substrate for 30 min at a 150 ℃ hot stage after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electron conducting layer.

3. Preparation of prolinamide doped perovskite light-absorbing layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide and 1mg of prolinamide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO so that the concentration of prolinamide is 1mg/ml, stirring while continuously heating at 70 ℃ for 12 hours by magnetic stirring, and then filtering with a syringe and filter combination to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by using a syringe and a filter tip combination to prepare an ammonium salt precursor solution;

3-3) preparing a lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at a rotation speed of 1500 rpm with an acceleration of 800m/s, and annealing at 70 ℃ for 1 minute to form a lead iodide layer after the spin-coating;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and preserving the heat for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparing proline modification layer on perovskite light absorption layer

4-1) preparation of proline modification layer solution

Mixing ultrapure water: DMF: DMSO =200 μ L: 700 μ L: 100 μ L1 mL of the mixed solvent was prepared, and 0.75mg of proline was added so that the proline concentration was 0.75mg/mL, and heated to 70 ℃ and stirred until dissolved;

4-2) spin coating 40 μ L of proline modification layer solution on the perovskite layer for 30 seconds at 4000 rpm in a nitrogen glove box, and then heat annealing at 75 ℃ for 1 minute, thereby preparing the proline modification layer.

5. Preparing hole conducting layer on proline modified layer

5-1) preparation of hole conducting layer solution: dissolving Li-TFSI by taking acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD in 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter combination to obtain a hole conducting layer solution;

5-2) preparing the hole conducting layer by spin coating 50 μ L of the hole conducting layer solution on the proline modifying layer in a nitrogen glove box at 4000 rpm for 30 seconds, placing the hole conducting layer on a culture dish after the spin coating is finished, and placing the culture dish in a drying box to oxidize for 24 hours under the air condition.

6. Preparing a metal electrode layer

And sputtering a metal silver (Ag) electrode on the hole conduction layer by using an evaporation method to prepare a metal electrode layer.

Example 2:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15 × 15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol after washing is finished, thus obtaining a cleaned conductive substrate;

1-4) drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution by using a liquid transfer gun, uniformly mixing with 2ml of deionized water, and filtering by combining an injector and a filter tip to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electron conducting layer solution by using a liquid transfer gun under air environment and room temperature, spin-coating the electron conducting layer solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the substrate for 30 min at a 150 ℃ hot stage after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electron conducting layer.

3. Preparation of prolinamide doped perovskite light-absorbing layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide and 0.5mg of prolinamide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO so that the concentration of prolinamide is 0.5mg/ml, stirring while continuously heating at 70 ℃ for 12 hours by magnetic stirring, and then filtering with a syringe and filter combination to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by combining an injector and a filter tip to prepare an ammonium salt precursor solution;

3-3) preparing a lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at 1500 rpm with an acceleration of 800m/s, and forming a lead iodide layer by annealing on a hot stage at 70 ℃ for 1 minute after the spin-coating is finished;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and preserving the heat for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparing proline modified layer on perovskite light absorption layer

4-1) preparation of proline modification layer solution

Mixing ultrapure water: DMF: DMSO =200 μ L700 μ L100 μ L1 mL mixed solvent was prepared, and 0.75mg proline was added, heated to 70 ℃ and stirred until dissolved;

4-2) spin coating 40 μ L of proline modification layer solution on the perovskite layer for 30 seconds at 4000 rpm in a nitrogen glove box, and then heat annealing at 75 ℃ for 1 minute, thereby preparing the proline modification layer.

5. Preparing a hole conducting layer on the proline modifying layer

5-1) preparation of hole conducting layer solution: dissolving Li-TFSI by using acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD by using 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter assembly to obtain a hole conducting layer solution;

5-2) preparing the hole conducting layer by spin coating 50 μ L of the hole conducting layer solution on the proline modifying layer in a nitrogen glove box at 4000 rpm for 30 seconds, placing the hole conducting layer on a culture dish after the spin coating is finished, and placing the culture dish in a drying box to oxidize for 24 hours under the air condition.

6. Preparing a metal electrode layer

And sputtering a metal silver (Ag) electrode on the hole conduction layer by using an evaporation method to prepare a metal electrode layer.

Example 3:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15 × 15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and after washing is finished, sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol to obtain a cleaned conductive base layer;

1-4) drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution and 2ml of deionized water by using a liquid transfer gun, uniformly mixing, and filtering by using a syringe and a filter tip combination to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electronic conducting layer solution by using a liquid transfer gun under the air environment and at room temperature, spin-coating the solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the conductive substrate in a hot stage at 150 ℃ for 30 min after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electronic conducting layer.

3. Preparation of prolinamide doped perovskite light-absorbing layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide and 1.5mg of prolinamide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO so that the concentration of prolinamide is 1.5mg/ml, continuously heating and stirring at 70 ℃ for 12 hours by magnetic stirring, and then filtering with a syringe and filter combination to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by combining an injector and a filter tip to prepare an ammonium salt precursor solution;

3-3) preparing a lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at a rotation speed of 1500 rpm with an acceleration of 800m/s, and annealing at 70 ℃ for 1 minute to form a lead iodide layer after the spin-coating;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and keeping the temperature for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparing proline modification layer on perovskite light absorption layer

4-1) preparation of proline modification layer solution

Mixing ultrapure water: DMF: DMSO =200 μ L: 700 μ L: 100 μ L1 mL of the mixed solvent was prepared, and 0.75mg of proline was added so that the proline concentration was 0.75mg/mL, heated to 70 ℃ and stirred until dissolved;

4-2) spin coating 40 μ L of proline modification layer solution on the perovskite layer for 30 seconds at 4000 rpm in a nitrogen glove box, and then heat annealing at 75 ℃ for 1 minute, thereby preparing the proline modification layer.

5. Preparing a hole conducting layer on the proline modifying layer

5-1) preparation of hole conducting layer solution: dissolving Li-TFSI by taking acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD by using 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter assembly to obtain a hole conducting layer solution;

5-2) spin coating 50 microliter of the hole conducting layer solution on the proline modification layer in a nitrogen glove box at the rotation speed of 4000 revolutions per minute for 30 seconds to prepare the hole conducting layer, placing the hole conducting layer into a culture dish after the spin coating is finished, and placing the culture dish into a drying box to oxidize for 24 hours under the air condition.

6. Preparing a metal electrode layer

And sputtering a metal silver (Ag) electrode on the hole conduction layer by using an evaporation method to prepare a metal electrode layer.

Example 4:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15 × 15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol after washing is finished, thus obtaining a cleaned conductive substrate;

1-4) drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution by using a liquid transfer gun, uniformly mixing with 2ml of deionized water, and filtering by combining an injector and a filter tip to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electron conducting layer solution by using a liquid transfer gun under air environment and room temperature, spin-coating the electron conducting layer solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the substrate for 30 min at a 150 ℃ hot stage after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electron conducting layer.

3. Preparation of prolinamide doped perovskite light-absorbing layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide and 1mg of prolinamide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO so that the concentration of prolinamide is 1mg/ml, stirring while continuously heating at 70 ℃ for 12 hours by magnetic stirring, and then filtering with a syringe and filter combination to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by combining an injector and a filter tip to prepare an ammonium salt precursor solution;

3-3) preparation of lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at 1500 rpm with an acceleration of 800m/s, and forming a lead iodide layer by annealing on a hot stage at 70 ℃ for 1 minute after the spin-coating is finished;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and preserving the heat for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparing proline modified layer on perovskite light absorption layer

4-1) preparation of proline modification layer solution

Mixing ultrapure water: DMF: DMSO =200 μ L: 700 μ L: 100 μ L1 mL of the mixed solvent was prepared, and 0.3mg of proline was added so that the proline concentration was 0.3mg/mL, heated to 70 ℃ and stirred until dissolved;

4-2) spin coating 40 μ L of proline modifying layer solution onto the perovskite layer in a nitrogen glove box at 4000 rpm for 30 seconds, and then heat annealing at 75 ℃ for 1 minute to prepare the proline modifying layer.

5. Preparing a hole conducting layer on the proline modifying layer

5-1) preparation of hole conducting layer solution: dissolving Li-TFSI by taking acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD in 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter combination to obtain a hole conducting layer solution;

5-2) preparing the hole conducting layer by spin coating 50 μ L of the hole conducting layer solution on the proline modifying layer in a nitrogen glove box at 4000 rpm for 30 seconds, placing the hole conducting layer on a culture dish after the spin coating is finished, and placing the culture dish in a drying box to oxidize for 24 hours under the air condition.

6. Preparing a metal electrode layer

The metal electrode layer was prepared by sputtering a metal silver (Ag) electrode on the hole conducting layer by an evaporation method.

Example 5:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15 × 15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and after washing is finished, sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol to obtain a cleaned conductive base layer;

1-4) drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution and 2ml of deionized water by using a liquid transfer gun, uniformly mixing, and filtering by using a syringe and a filter tip combination to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electron conducting layer solution by using a liquid transfer gun under air environment and room temperature, spin-coating the electron conducting layer solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the substrate for 30 min at a 150 ℃ hot stage after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electron conducting layer.

3. Preparation of prolinamide doped perovskite light-absorbing layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide and 1mg of prolinamide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO so that the concentration of prolinamide is 1mg/ml, stirring while continuously heating at 70 ℃ for 12 hours by magnetic stirring, and then filtering with a syringe and filter combination to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by combining an injector and a filter tip to prepare an ammonium salt precursor solution;

3-3) preparation of lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at 1500 rpm with an acceleration of 800m/s, and forming a lead iodide layer by annealing on a hot stage at 70 ℃ for 1 minute after the spin-coating is finished;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and preserving the heat for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparing proline modified layer on perovskite light absorption layer

4-1) preparation of proline modification layer solution

Mixing ultrapure water: DMF: DMSO =200 μ L: 700 μ L: 100 μ L1 mL of the mixed solvent was prepared, and 1.2mg of proline was added so that the proline concentration was 1.2mg/mL, and heated to 70 ℃ and stirred until dissolved;

4-2) spin coating 40 μ L of proline modification layer solution on the perovskite layer for 30 seconds at 4000 rpm in a nitrogen glove box, and then heat annealing at 75 ℃ for 1 minute, thereby preparing the proline modification layer.

5. Preparing a hole conducting layer on the proline modifying layer

5-1) preparation of hole conducting layer solution: dissolving Li-TFSI by using acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD in 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter combination to obtain a hole conducting layer solution;

5-2) spin coating 50 microliter of the hole conducting layer solution on the proline modification layer in a nitrogen glove box at the rotation speed of 4000 revolutions per minute for 30 seconds to prepare the hole conducting layer, placing the hole conducting layer into a culture dish after the spin coating is finished, and placing the culture dish into a drying box to oxidize for 24 hours under the air condition.

6. Preparing a metal electrode layer

And sputtering a metal silver (Ag) electrode on the hole conduction layer by using an evaporation method to prepare a metal electrode layer.

Comparative example 1:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15 × 15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol after washing is finished, thus obtaining a cleaned conductive substrate;

1-4) drying the cleaned conductive substrate layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution and 2ml of deionized water by using a liquid transfer gun, uniformly mixing, and filtering by using a syringe and a filter tip combination to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electron conducting layer solution by using a liquid transfer gun under air environment and room temperature, spin-coating the electron conducting layer solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the substrate for 30 min at a 150 ℃ hot stage after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electron conducting layer.

3. Preparation of prolinamide doped perovskite light absorption layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO, continuously heating and stirring at 70 ℃ for 12 hours by using magnetic stirring, and then filtering by using a combination of an injector and a filter tip to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by combining an injector and a filter tip to prepare an ammonium salt precursor solution;

3-3) preparation of lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at 1500 rpm with an acceleration of 800m/s, and forming a lead iodide layer by annealing on a hot stage at 70 ℃ for 1 minute after the spin-coating is finished;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and preserving the heat for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparation of hole conducting layer in perovskite light-absorbing layer

4-1) preparation of hole conducting layer solution: dissolving Li-TFSI by taking acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD in 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter combination to obtain a hole conducting layer solution;

5-2) preparing the hole conducting layer by spin coating 50 μ L of the hole conducting layer solution on the proline modifying layer in a nitrogen glove box at 4000 rpm for 30 seconds, placing the hole conducting layer on a culture dish after the spin coating is finished, and placing the culture dish in a drying box to oxidize for 24 hours under the air condition.

5. Preparing a metal electrode layer

And sputtering a metal silver (Ag) electrode on the hole conduction layer by using an evaporation method to prepare a metal electrode layer.

Comparative example 2:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15 × 15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol after washing is finished, thus obtaining a cleaned conductive substrate;

1-4) drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution and 2ml of deionized water by using a liquid transfer gun, uniformly mixing, and filtering by using a syringe and a filter tip combination to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electronic conducting layer solution by using a liquid transfer gun under the air environment and at room temperature, spin-coating the solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the conductive substrate in a hot stage at 150 ℃ for 30 min after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electronic conducting layer.

3. Preparation of prolinamide doped perovskite light-absorbing layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide and 10mg of prolinamide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO so that the concentration of prolinamide is 10mg/ml, continuously heating and stirring at 70 ℃ for 12 hours by magnetic stirring, and then filtering with a syringe and filter combination to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by combining an injector and a filter tip to prepare an ammonium salt precursor solution;

3-3) preparation of lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at a rotation speed of 1500 rpm with an acceleration of 800m/s, and annealing at 70 ℃ for 1 minute to form a lead iodide layer after the spin-coating;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and keeping the temperature for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparing proline modified layer on perovskite light absorption layer

4-1) preparation of proline modification layer solution

Mixing ultrapure water: DMF: DMSO =200 μ L: 700 μ L: 100 μ L1 mL of the mixed solvent was prepared, and 0.75mg of proline was added so that the proline concentration was 0.75mg/mL, and heated to 70 ℃ and stirred until dissolved;

4-2) spin coating 40 μ L of proline modifying layer solution onto the perovskite layer in a nitrogen glove box at 4000 rpm for 30 seconds, and then heat annealing at 75 ℃ for 1 minute to prepare the proline modifying layer.

5. Preparing hole conducting layer on proline modified layer

5-1) preparation of hole conducting layer solution: dissolving Li-TFSI by taking acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD by using 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter assembly to obtain a hole conducting layer solution;

5-2) spin coating 50 microliter of the hole conducting layer solution on the proline modification layer in a nitrogen glove box at the rotation speed of 4000 revolutions per minute for 30 seconds to prepare the hole conducting layer, placing the hole conducting layer into a culture dish after the spin coating is finished, and placing the culture dish into a drying box to oxidize for 24 hours under the air condition.

6. Preparing a metal electrode layer

And sputtering a metal silver (Ag) electrode on the hole conduction layer by using an evaporation method to prepare a metal electrode layer.

Comparative example 3:

1. conductive base layer treatment

1-1) preparing a substrate cleaning solution: uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to a volume ratio of 30;

1-2) ITO conductive glass with sheet resistance of 15 and transmittance of 93%, and substrate size of 15 × 15mm ² 0.7 mm thick;

1-3) carrying out partition treatment on the conductive substrate by utilizing laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing by using deionized water and absolute ethyl alcohol, and after washing is finished, sequentially carrying out ultrasonic cleaning by using the substrate cleaning solution, ethyl alcohol, deionized water, acetone and ethyl alcohol to obtain a cleaned conductive base layer;

1-4) drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment for 15 minutes.

2. Preparing an electron-conducting layer on a conductive base layer

2-1) preparing an electron conducting layer solution: taking 500 mu L of tin dioxide nanocrystal solution by using a liquid transfer gun, uniformly mixing with 2ml of deionized water, and filtering by combining an injector and a filter tip to obtain an electronic conducting layer solution;

2-2) taking 70 mu L of electron conducting layer solution by using a liquid transfer gun under air environment and room temperature, spin-coating the electron conducting layer solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the substrate for 30 min at a 150 ℃ hot stage after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electron conducting layer.

3. Preparation of prolinamide doped perovskite light absorption layer on electron conducting layer

3-1) preparing lead iodide precursor solution: dissolving 600mg of lead iodide and 1mg of prolinamide in a mixed solvent of 900. Mu.L of DMF and 100. Mu.L of DMSO so that the concentration of prolinamide is 1mg/ml, stirring while continuously heating at 70 ℃ for 12 hours by magnetic stirring, and then filtering with a syringe and filter combination to prepare a lead iodide precursor solution;

3-2) preparing ammonium salt precursor solution: dissolving 60mgFAI, 6mgMACl and 6mgMABr in proportion by taking 1ml of isopropanol as a solvent, and then filtering by combining an injector and a filter tip to prepare an ammonium salt precursor solution;

3-3) preparing a lead iodide layer: spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at 1500 rpm with an acceleration of 800m/s, and forming a lead iodide layer by annealing on a hot stage at 70 ℃ for 1 minute after the spin-coating is finished;

3-4) preparing a perovskite light absorption layer: and after the surface is blown by nitrogen, coating 100 mu L of ammonium salt precursor solution on the lead iodide layer in a rotating speed of 1500-1700 rpm, heating the lead iodide layer in a nitrogen glove box at 70 ℃ for 50-60 seconds, heating the lead iodide layer to 150 ℃ in an indoor air environment with the humidity of 45-60%, and keeping the temperature for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

4. Preparation of hole conducting layer in perovskite light-absorbing layer

4-1) preparation of hole conducting layer solution: dissolving Li-TFSI by using acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml; dissolving 0.0723g of Spiro-MeOTAD by using 1ml of chlorobenzene as a solvent, adding 28.5 mu L of tBP and 17.5 mu L of Li-TFSI acetonitrile solution, stirring for 1 hour, and filtering by using a syringe and filter assembly to obtain a hole conducting layer solution;

4-2) preparing the hole conducting layer by spin coating 50 μ L of the hole conducting layer solution on the proline modifying layer for 30 seconds in a nitrogen glove box at 4000 rpm, placing the hole conducting layer solution into a culture dish after the spin coating is finished, and placing the culture dish into a drying box to oxidize for 24 hours under the air condition.

5. Preparing a metal electrode layer

And sputtering a metal silver (Ag) electrode on the hole conduction layer by using an evaporation method to prepare a metal electrode layer.

The effect example:

the perovskite solar cells of examples 1 to 5 and comparative examples 1 to 3 were subjected to J-V curve tests as shown in fig. 2 and 3.

Quantum Efficiency (EQE) tests, electrochemical Impedance (EIS) tests, dark-state current density-voltage (Dark J-V) curve tests, space charge-limited current method (SCLC) tests, X-ray diffraction (XRD) tests, ultraviolet-visible absorption spectra and Tacu-plot, ultraviolet photoelectron spectra, and photoelectric conversion efficiency stability tests of the perovskite solar cells obtained in example 1 and comparative example 1 were performed, respectively, as shown in fig. 4 to fig. 14. The test results are as follows:

the perovskite solar cell prepared in example 1 has an average photoelectric conversion efficiency of 22.52% and a maximum photoelectric conversion efficiency of 22.97% under a simulated sunlight environment.

The perovskite solar cell prepared in example 2 has an average photoelectric conversion efficiency of 20.89% and a maximum photoelectric conversion efficiency of 21.13% under a simulated sunlight environment.

The perovskite solar cell prepared in example 3 has an average photoelectric conversion efficiency of 21.56% and a maximum photoelectric conversion efficiency of 21.70% under a simulated sunlight environment.

The perovskite solar cell prepared in example 4 has an average photoelectric conversion efficiency of 21.32% and a maximum photoelectric conversion efficiency of 21.79% under a simulated sunlight environment.

The perovskite solar cell prepared in example 5 has an average photoelectric conversion efficiency of 21.24% and a maximum photoelectric conversion efficiency of 21.65% when detected in a simulated sunlight environment.

The perovskite solar cell prepared in the comparative example 1 has an average photoelectric conversion efficiency of 18.97% and a highest photoelectric conversion efficiency of 19.25% when detected in a simulated sunlight environment.

The perovskite solar cell prepared in the comparative example 2 has an average photoelectric conversion efficiency of 19.79% and a maximum photoelectric conversion efficiency of 20.44% under the simulated sunlight environment. The reason for this may be that the doping amount is too high, so that the additive destroys the crystal lattice structure of the perovskite, and further affects the normal transport of the current carrier, thereby causing the additive to have an adverse effect on the photoelectric properties of the device.

The perovskite solar cell prepared in the comparative example 3 has the average photoelectric conversion efficiency of 20.60% and the highest photoelectric conversion efficiency of 20.82% under the simulated sunlight environment.

In addition, the performance of example 1 was compared to comparative example 1 as follows:

as can be seen from fig. 4, the quantum efficiency of the perovskite solar cell prepared in example 1 was higher than that of comparative example 1 in which prolinamide addition and proline modification were not performed, and the integrated current density-wavelength curve obtained by the quantum efficiency is also included in fig. 4, and it can be found that the integrated current density of example 1 (23.26 mA/cm) ² ) Higher than that of comparative example 1 (22.78 mA/cm) ² ) And is consistent with the current density-voltage test results.

As can be seen from fig. 5, the interfacial transport resistance of the device after prolinamide and proline treatment (example 1) was reduced from 17.4 k Ω to 8.7 k Ω, indicating that the carriers in the normal transport process received less interfacial hindrance and that the interfacial defects between the electron conducting layer and the perovskite layer and between the hole conducting layer and the perovskite layer were passivated.

As can be seen from FIG. 6, the dark state leakage current after prolinamide and proline treatment (example 1) is significantly reduced, indicating that the loss of the effective current is reduced.

As can be seen from FIGS. 7 and 8, the voltage (V) corresponding to the intersection of the two fitting lines _TFL ) The defect state density of the perovskite layer material in comparative example 1 was calculated as: 1.29X 10 ¹⁶ /cm ² Whereas the defect state density of the perovskite layer material in example 1 is reduced as follows: 9.98X 10 ¹⁵ /cm ² 。

The 12.8 ℃ diffraction peak in FIG. 9 belongs to PbI ₂ And the diffraction peak of about 14.2 degrees belongs to the characteristic peak of the (110) crystal face of the perovskite. Which shows doping of prolinamides and post-proline modification unreacted residual perovskite precursor PbI ₂ Less, and the perovskite layer material has higher characteristic diffraction peak and stronger crystallinity.

As can be seen from fig. 10, the absorption capacity of the perovskite layer after prolinamide treatment (example 1) was enhanced, and the forbidden bandwidth of the perovskite layer material before prolinamide treatment (example 1) (comparative example 1) was calculated using the Tacu-plot method and fitted to be 1.583eV and 1.579eV, respectively; meanwhile, the valence band top energy levels of the perovskite layer before and after prolinamide treatment are obtained by curve fitting in the graph shown in FIG. 11 to be-5.89 eV and-5.79 eV, and the conduction band bottom energy levels of the perovskite layer before and after prolinamide treatment are obtained by combining the forbidden band width of the perovskite layer to be-4.277 eV and-4.21 eV; after the prolinamide treatment, the energy level of the perovskite layer material is shifted upwards, which is more favorable for the transmission of electrons to the electron conducting layer through the energy level matching effect.

As shown in fig. 12 to 14, with respect to the perovskite solar cell obtained in example 1, the photoelectric conversion efficiency after 720 hours of dark storage in a nitrogen glove box environment was 21.21%, the photoelectric conversion efficiency after 240 hours of continuous irradiation with a standard solar intensity was 18.24%, and the photoelectric conversion efficiency after 720 hours of storage in an air environment with a humidity of 40% to 60% was 16.85%; the perovskite solar cell obtained in the comparative example 1 has a photoelectric conversion efficiency of 15.82% after being stored in a nitrogen glove box environment for 720 hours in a dark place; the photoelectric conversion efficiency is 7.84% after continuous irradiation for 240 hours by using standard solar intensity; the photoelectric conversion efficiency is 10.81% after 720 hours of storage in an air environment with the humidity of 40% -60%. It has poor stability.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A method for preparing a perovskite solar cell through crystallization regulation, which is characterized by comprising the following steps:

(1) Drying the cleaned conductive base layer by using nitrogen and carrying out ultraviolet-ozone treatment;

(2) Preparing an electron conducting layer on the conductive base layer;

(3) Preparing a prolinamide calcium doped perovskite light absorption layer on the electron conducting layer;

(4) Preparing a proline modifying layer on the perovskite light absorption layer;

(5) Preparing a hole conducting layer on the proline modifying layer;

(6) And sputtering a metal electrode on the hole conduction layer by using a magnetron sputtering instrument or an evaporation method to prepare a metal electrode layer.

2. The method for preparing a perovskite solar cell through crystallization regulation according to claim 1, wherein the step (1) comprises:

after the conductive substrate is subjected to partition treatment by laser engraving, scrubbing the conductive substrate by using non-woven fabrics soaked in the substrate cleaning solution, then sequentially washing the conductive substrate by using deionized water and absolute ethyl alcohol, and sequentially and respectively ultrasonically cleaning the conductive substrate for 15min by using the substrate cleaning solution, the ethyl alcohol, the deionized water, the acetone and the ethyl alcohol after washing is finished to obtain a cleaned conductive base layer;

the substrate cleaning liquid is obtained by uniformly mixing deionized water, a glass cleaning agent and a liquid detergent according to the volume ratio of 30.

3. The method for preparing a perovskite solar cell through crystallization regulation according to claim 1, wherein the step (2) comprises:

taking 70 mu L of electronic conducting layer solution by using a liquid transfer gun at air environment and room temperature, spin-coating the solution on the conductive substrate at the spin-coating speed of 3000 r/min, annealing the conductive substrate at a hot stage at 150 ℃ for 30 min after the spin-coating is finished, and then carrying out ultraviolet-ozone treatment to prepare the electronic conducting layer;

the electronic conducting layer solution is obtained by uniformly mixing a tin dioxide nanocrystal solution and deionized water according to the proportion of 1.

4. The method for preparing a perovskite solar cell subjected to crystallization regulation according to claim 1, wherein the step (3) comprises the following steps:

spin-coating 80-100 μ L of lead iodide precursor solution onto an electron conducting layer in a nitrogen glove box at 1500 rpm with an acceleration of 800m/s, and forming a lead iodide layer by annealing on a hot stage at 70 ℃ for 1 minute after the spin-coating is finished;

after the surface is blown by nitrogen, 100-110 mu L of ammonium salt precursor solution is spin-coated on the lead iodide layer at the rotating speed of 1500-1700 rpm; heating the mixture in a nitrogen glove box at 70 ℃ for 50-60 seconds, then heating the mixture to 150 ℃ in an indoor air environment with the humidity of 45-60%, and preserving the heat for 15 minutes to obtain the prolinamide doped perovskite light absorption layer.

5. The method for preparing a perovskite solar cell with crystallization regulation according to claim 4, wherein the lead iodide precursor solution is prepared by mixing lead iodide and prolinamide according to a certain proportion, adding the mixture into a solvent of N, N-dimethylformamide and dimethyl sulfoxide mixed with a solvent ratio of 9.

6. The method for preparing the perovskite solar cell through crystallization regulation and control as claimed in claim 4, wherein the ammonium salt precursor solution is obtained by adding iodoformamidine, chloromethylamine and bromomethylamine in a mass ratio of (9-10): 2-1): 1 into an isopropanol solution, dissolving, and filtering through a syringe and filter tip combination.

7. The method for preparing the perovskite solar cell subjected to crystallization regulation according to claim 1, wherein the step (4) comprises the following steps:

adding proline into a mixed solvent obtained by mixing ultrapure water, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 2;

40 μ L of the proline modifying layer solution was spin coated on the perovskite layer in a nitrogen glove box at 4000 rpm for 30 seconds, and then heat annealed at 75 ℃ for 1 minute to prepare the proline modifying layer.

8. The method for preparing a perovskite solar cell subjected to crystallization regulation according to claim 1, wherein the step (5) comprises the following steps: and (3) spin-coating 50 mu L of the hole conducting layer solution on the proline modification layer for 30 seconds in a nitrogen glove box at the rotating speed of 4000 rpm to prepare the hole conducting layer, and placing the hole conducting layer into a drying box to oxidize for 24 hours after the spin-coating is finished.

9. The method for preparing a perovskite solar cell subjected to crystallization regulation according to claim 1, wherein the hole conducting layer solution is prepared by the following method:

dissolving Li-TFSI by using acetonitrile as a solvent to prepare a Li-TFSI acetonitrile solution with the concentration of 520 mg/ml;

dissolving Spiro-OMeTAD in chlorobenzene as a solvent, adding tBP and the Li-TFSI acetonitrile solution, and filtering by combining a syringe and a filter tip to obtain the product.

10. A perovskite solar cell as defined in any one of claims 1 to 9.

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