Modified hole transport layer material and perovskite solar cells fabricated therefrom

Abstract

This invention provides a modified hole transport layer material and a perovskite solar cell manufactured therefrom. [Solution] The modified hole transport layer material is a hole transport layer material modified using a highly polar amphiphilic material. The amphiphilic material can form an amphiphilic layer between PTAA and perovskite, and the highly polar structure of the amphiphilic material improves the wettability of polar solvents on its surface and improves the film formation of perovskite precursors on the PTAA surface. In addition, heteroatoms such as S and O in the molecule bind to free lead ions in the perovskite and play a role in passivation of the lower interface.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This disclosure claims priority to a Chinese patent application filed with the Chinese National Intellectual Property Office on 13 February 2025, application number CN202510159385.4, titled "Modified Hole Transport Layer Material and Perovskite Solar Cell Manufactured Thereof," the entire contents of which are incorporated herein by reference.

[0002] This application relates to the art of solar cells, and more particularly to modified hole transport layer materials and perovskite solar cells manufactured therefrom. [Background technology]

[0003] Perovskite solar cells have become a focus of research in the global solar cell field in recent years due to their significant advantages, including low manufacturing costs and high efficiency. Transperovskite solar cells are one type of perovskite solar cell structure, and their basic structure consists of a transparent conductive electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a metal electrode. Among these, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA) perovskite is a hole transport material commonly used in solar cells.

[0004] However, due to its low molecular polarity, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) has extremely poor wettability to higher perovskite precursor solutions, such as DMF and DMSO. As a result, inconsistencies exist in the perovskite manufacturing process, affecting contact at the region interface and leading to a decrease in device performance, which is also disadvantageous for the industrial manufacturing of large-area devices. [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of this application is to provide a modified hole transport layer material and a perovskite solar cell manufactured therefrom, which can improve the wettability to organic solvents and the film deposition quality of perovskite by modifying the PTAA surface with an amphiphilic material, and which can also improve the photoelectric conversion efficiency of perovskite solar cells by having heteroatoms such as S and O in such a material to play a role in passivation of the lower interface of the perovskite. [Means for solving the problem]

[0006] To achieve the above objective, this application provides a modified hole transport layer material, which is a hole transport layer material modified with a highly polar amphiphilic material.

[0007] The present invention further provides a perovskite solar cell comprising, in order, a transparent conductive substrate, a hole transport layer on which a modified hole transport layer material is deposited, a perovskite layer, an electron transport layer, and a metal electrode, all arranged in layers.

[0008] The present application relates to a method for manufacturing a perovskite solar cell, The process involves depositing poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] onto a cleaned transparent conductive substrate, and spin-coating an amphiphilic material solution onto the poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] to obtain an amphiphilic layer, and The present invention further provides a manufacturing method comprising the step of sequentially depositing a perovskite layer material, an electron transport layer material, and metal electrodes on an amphiphilic layer to obtain a perovskite solar cell. [Effects of the Invention]

[0009] Technical effects and advantages of this application The amphiphilic material used in the present application can form an amphiphilic layer between PTAA and perovskite. The high-polarity structure of the amphiphilic material improves the wettability of the polar solvent on its surface and the film-forming property of the perovskite precursor on the PTAA surface. In addition, heteroatoms such as S and O in the molecule bind to the free lead ions in the perovskite and play a role in passivating the lower interface.

[0010] Other features and advantages of the present application will be described in the following description, and will be partially apparent from the specification or will be understood by the implementation of the present application.

Brief Description of the Drawings

[0011] To more clearly explain the technical solutions in the embodiments or related technologies of the present application, the drawings necessary for the description of the embodiments or related technologies will be briefly described below. The drawings in the following description are some embodiments of the present application, and it is obvious to those skilled in the art that other drawings can be obtained based on these drawings without creative efforts. [Figure 1] It is a flowchart of a method for manufacturing a perovskite solar cell.

Modes for Carrying Out the Invention

[0012] Hereinafter, referring to the drawings in the embodiments of the present application, the technical solutions in the embodiments of the present application will be clearly and completely described. It is obvious that the described embodiments are only a part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present application.

[0013] Note that the structures, proportions, sizes, etc. shown in the drawings attached to this specification are only used for those skilled in the art to understand and read in accordance with the content disclosed in the specification, and are not for limiting the feasible limiting conditions of the present application. Therefore, they do not have any substantial technical significance. Any modification of the structure, change of the proportional relationship, or adjustment of the size should fall within the scope of the technical content disclosed in the present application as long as it does not affect the effects that the present application can generate and the objectives that can be achieved. In addition, terms such as "upper", "lower", "left", "right", "middle", and "one" cited in this specification are also for facilitating the clarification of the description and are not for limiting the feasible scope of the present application. Any change or adjustment of their relative relationships should be regarded as within the feasible scope of the present application as long as it does not substantially change the technical content.

[0014] The present application provides a modified hole transport layer material which is a hole transport layer material modified with an amphiphilic material having a high-polarity structure.

[0015] Examples of the amphiphilic material include materials having a high sulfonic acid structure such as sodium linear alkylbenzene sulfonate (LAS), sodium fatty alcohol polyoxyethylene ether sulfate (AES), ammonium fatty alcohol polyoxyethylene ether sulfate (AESA), sodium lauryl alcohol sulfate, lignosulfonate, heavy alkylbenzene sulfonate, alkyl sulfonate (petroleum sulfonate), dispersant NNO, dispersant MF, etc.; polyether-based materials such as alkyl polyether (PO-EO copolymer), fatty alcohol polyoxyethylene ether (AEO-3), nonylphenol polyoxyethylene ether (TX-10), etc.; and amino acid-based materials such as lauroyl glutamate.

[0016] The hole transport layer material is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine].

[0017] The present invention further provides a perovskite solar cell comprising, in order, a transparent conductive substrate, a hole transport layer on which a modified hole transport layer material is deposited, a perovskite layer, an electron transport layer, and a metal electrode, all arranged in layers.

[0018] The present invention also provides a method for manufacturing a perovskite solar cell. As shown in Figure 1, the method includes the steps of: cleaning a transparent conductive substrate; depositing poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] on the cleaned transparent conductive substrate; spin-coating an amphiphilic material solution onto the poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] to obtain an amphiphilic layer; and sequentially depositing a perovskite layer material, an electron transport layer material, and metal electrodes on the amphiphilic layer to obtain a perovskite solar cell.

[0019] The step of obtaining the transparent conductive substrate after cleaning includes the steps of sequentially ultrasonically cleaning the transparent conductive substrate with deionized water, isopropanol, and acetone, and blow-drying the transparent conductive substrate after ultrasonic cleaning and UV treatment.

[0020] The transparent conductive substrate includes one of ITO substrate, FTO substrate, or AZO substrate.

[0021] The amphiphilic material solution has a concentration of 1 mg / mL to 50 mg / mL, and the amount used is determined according to the area of ​​the transparent conductive substrate.

[0022] The deposition thickness of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] is 10-50 nm.

[0023] The aforementioned perovskite layer material is Cs x MA y FA 1-x-y Pb(I a Br 1-a )3, the deposition thickness is 300~800nm, and the range of x, y, and a values ​​is 0~1.

[0024] The electron transport layer material includes one or more of [6,6]-phenyl-C 61 -isomethyl butyrate (PC 61 BM), fullerene (C 60 ), bathocuproine (BCP), and has a deposition thickness of 5 - 30 nm.

[0025] The metal electrode includes any one of Au, Ag, Cu, and Al, and the thickness of the metal electrode is 50 - 300 nm.

[0026] To better explain this solution, the following examples are provided. Example 1

[0027] A method for manufacturing a perovskite solar cell, including the following steps.

[0028] 1. An ITO (indium tin oxide) substrate with a size of 2.5 * 2.5 cm was sequentially ultrasonically cleaned with deionized water, isopropyl alcohol, and acetone for 15 minutes each, then the ITO substrate was blown dry with nitrogen gas and subjected to UV treatment for 30 minutes.

[0029] 2. Onto the cleaned ITO glass, a chlorobenzene (CB) solution of PTAA was spin-coated at a rotation speed of 4000 rpm for 30 seconds. After the spin coating, annealing was performed at 120 °C for 20 minutes to obtain a PTAA hole transport layer.

[0030] 3. Preparation of a sodium linear alkylbenzene sulfonate (LAS) solution: 20 mg of LAS was dissolved in 1 mL of methanol (IPA).

[0031] 4. Preparation of an amphiphilic layer: The prepared LAS solution was spin-coated onto the PTAA film layer at a rotation speed of 3000 rpm for 40 seconds. After the spin coating, annealing was performed at 100 °C for 10 minutes to obtain an amphiphilic layer.

[0032] 5. Cs 0.05 (FA 0.85 MA 0.15)0.95 Pb(I 0.85 Br 0.153. Preparation of perovskite precursor solution: Mix DMF and DMSO in an 8.5:1.5 ratio and add CsI, FAI, MAI, PbI2, and PbBr2 in a molar ratio of 0.05:0.81:0.14:0.78:0.22. 0.05 (Fa 0.85 MA 0.15)0.95 Pb(I 0.85 Br 0.15 )3 was dissolved at a molar volume ratio of 1.4 mol / liter, stirred for 3 hours, and prepared for use. A perovskite absorption layer was prepared by spin coating at a rotation speed of 5000 rpm and a spin coating time of 40 seconds. At the 33-second spin coating stage, the poor solvent CB was added dropwise, and the mixture was annealed at 120°C for 30 minutes to obtain the perovskite absorption layer.

[0033] 6. Manufacturing of the electron transport layer: PC in a sample vial 61 20 mg of BM powder was weighed, and 1 mL of chlorobenzene was added. The mixture was stirred for 12 hours to prepare it for use. It was then applied by spin coating at a rotation speed of 1500 rpm for 30 seconds using the spin coating method. 61 A BM electron transport layer was fabricated, and a 0.5 mg / mL BCP solution was spin-coated onto the electron transport layer at a rotation speed of 5000 rpm for 30 seconds. After spin-coating was complete, the layer was annealed at 100°C for 7 minutes.

[0034] 7. Electrode Ag was deposited to a thickness of 100 nm. Example 2

[0035] A method for manufacturing a perovskite solar cell, comprising the following steps:

[0036] 1. A 2.5 x 2.5 cm ITO substrate was ultrasonically cleaned sequentially with deionized water, isopropyl alcohol, and acetone for 15 minutes each. The ITO substrate was then blow-dried with nitrogen gas and UV treated for 30 minutes.

[0037] 2. A chlorobenzene (CB) solution of PTAA was spin-coated onto the washed ITO glass at a rotation speed of 4000 rpm for 30 seconds. After spin-coating was completed, the glass was annealed at 120°C for 20 minutes to obtain a PTAA hole transport layer.

[0038] 3. Preparation of fatty alcohol polyoxyethylene ether sodium sulfate (AES) solution: 3 mg of AES was dispersed in 1 mL of propylene glycol.

[0039] 4. Preparation of the amphiphilic layer: The prepared AES solution was spin-coated onto the PTAA film layer at a rotational speed of 3000 rpm for 40 seconds. After spin-coating was completed, the mixture was annealed at 120°C for 10 minutes to obtain the amphiphilic layer.

[0040] 5.Cs 0.05 (Fa 0.85 MA 0.15 ) 0.95 Pb(I 0.85 Br 0.15 3. Preparation of perovskite precursor solution: Mix DMF and DMSO in an 8.5:1.5 ratio and add CsI, FAI, MAI, PbI2, and PbBr2 in a molar ratio of 0.05:0.81:0.14:0.78:0.22. 0.05 (Fa 0.85 MA 0.15 ) 0.95 Pb(I 0.85 Br 0.15 )3 was dissolved at a molar volume ratio of 1.4 mol / liter and stirred for 3 hours to prepare for use. A perovskite absorbent layer was prepared by spin coating at a rotation speed of 5000 rpm and a spin coating time of 40 seconds. At the pin coating point of 33 seconds, the poor solvent CB was added dropwise, and the mixture was annealed at 120°C for 30 minutes to obtain the perovskite absorbent layer.

[0041] 6. Manufacturing of the electron transport layer: The device with the manufactured perovskite absorption layer is transferred to the deposition apparatus, and sequentially, C 60 The material was deposited at a rate of 0.03 nm / s to a thickness of 15 nm, and BCP was deposited at a rate of 0.02 nm / s to a thickness of 6 nm, with a deposition vacuum of 4E to 4 Pa.

[0042] 7. Electrode Ag was deposited to a thickness of 100 nm.

[0043] The above are merely preferred embodiments of the present application and do not limit it. While the present application has been described in detail with reference to the above embodiments, those skilled in the art can modify the technical solutions described in each of the above embodiments or replace some of their technical features with equivalents. Any modifications, equivalent replacements, improvements, etc., made within the spirit and principles of the present application should be included within the scope of protection.

Claims

1. A modified hole transport layer material characterized by being a hole transport layer material modified with an amphiphilic material with a highly polar structure.

2. The amphiphilic material comprises at least one of the following: sodium linear alkylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, ammonium fatty alcohol polyoxyethylene ether sulfate, sodium lauryl alcohol sulfate, lauroyl glutamic acid, nonylphenol polyoxyethylene ether, monoglyceride stearate, lignin sulfonate, dialkylbenzene sulfonate, alkyl sulfonate, diffusion agent NNO, diffusion agent MF, alkyl polyether, and fatty alcohol polyoxyethylene ether, as described in claim 1.

3. The modified hole transport layer material according to claim 1, wherein the hole transport layer material is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine].

4. A perovskite solar cell manufactured with the modified hole transport layer material described in claim 1, A perovskite solar cell characterized by comprising, in order, a transparent conductive substrate, a hole transport layer on which a modified hole transport layer material is deposited, a perovskite layer, an electron transport layer, and a metal electrode, all arranged in layers.

5. A method for manufacturing a perovskite solar cell according to claim 4, The process involves depositing poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] onto a cleaned transparent conductive substrate, and then spin-coating an amphiphilic material solution onto the poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] to obtain an amphiphilic layer, and A manufacturing method characterized by comprising the step of sequentially depositing a perovskite layer material, an electron transport layer material, and a metal electrode on an amphiphilic layer to obtain a perovskite solar cell.

6. The step of obtaining the transparent conductive substrate after washing is, The steps include sequentially ultrasonically cleaning a transparent conductive substrate with deionized water, isopropanol, and acetone, The method according to claim 5, comprising the steps of blow-drying a transparent conductive substrate after ultrasonic cleaning and UV treatment.

7. The method according to claim 5, wherein the transparent conductive substrate includes any one of an ITO substrate, an FTO substrate, or an AZO substrate.

8. The method according to claim 5, wherein the concentration of the amphiphilic material solution is 1 mg / mL to 50 mg / mL.

9. The method according to claim 5, wherein the deposition thickness of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] is 10 to 50 nm.

10. The perovskite layer material is Cs ｘ MA ｙ FA １－ｘ－ｙ Pb(I ａ Br １－ａ ) ３ The depositional thickness is 300 to 800 nm. The method according to claim 5, wherein the range of values ​​for x, y, and a is 0 to 1.

11. The electron transport layer material is [6,6]-phenyl-C ６１ - The method according to claim 5, comprising at least one of isomethyl butyrate, fullerene, and bathocuproine, with a deposition thickness of 5 to 30 nm.

12. The manufacturing method according to claim 5, wherein the metal electrode comprises any of Au, Ag, Cu, and Al, and the thickness of the metal electrode is 50 to 300 nm.

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