Hole transport layer and preparation method thereof, solar cell and preparation method thereof, photovoltaic module

Abstract

The application relates to the technical field of solar cells, in particular to a hole transport layer and a preparation method thereof, a solar cell and a preparation method thereof, and a photovoltaic module. The hole transport layer provided by the embodiment of the application comprises a phosphazene carbazole derivative containing a triazole ring, so that the hole transport layer has good uniformity, can effectively passivate defects of a substrate, can reduce the problem of leakage current, can avoid the problem of moisture absorption when a small molecule is directly used, improves the stability of the hole transport layer, and prolongs the service life of a device.

Description

Technical Field

[0001] This application relates to the field of solar cell technology, and in particular to hole transport layers and their preparation methods, solar cells and their preparation methods, and photovoltaic modules. Background Technology

[0002] As a novel photovoltaic device with broad application prospects, perovskite solar cells have achieved a leapfrog improvement in photoelectric conversion efficiency over the past decade, thanks to the continuous development of perovskite film deposition technology and its own material technology. Efficiency has increased dramatically from the initial 3.8% to over 26%, demonstrating enormous commercial potential. In the industrialization process of perovskite solar cells, the performance of charge transport materials plays a crucial role. Among them, the high efficiency, stability, and low cost of hole transport materials (HTMs) are core elements driving the commercial application of perovskite solar cells. Therefore, the research and development of related materials and fabrication processes have attracted much attention. Currently, anchor-based self-assembly strategies have been proven to be used to construct hole transport layers (HTLs) for high-performance pin-structured perovskite solar cells. Specifically, using molecular hole transport materials containing anchoring groups (such as carboxyl groups) allows for spontaneous adsorption onto the oxide substrate surface, forming a single-layer hole transport layer. Compared to the thick hole transport layers prepared by traditional methods such as spin coating or spray pyrolysis, the single-layer hole transport layer structure has the advantages of lower material consumption and lower parasitic absorption. Furthermore, chemical bath deposition, as a low-cost and easily scalable process, has been successfully applied to the fabrication of small modules and large-area perovskite silicon tandem solar cells.

[0003] However, although the hole transport layer fabrication technology based on the self-assembly strategy has made some progress, the reported single self-assembled molecular layers have poor uniformity in the large-area fabrication process, which leads to leakage current in the battery device and seriously affects the photoelectric performance and stability of the battery device. The application of hole transport layer fabrication based on the self-assembly strategy in the large-scale production of perovskite solar cells has brought great obstacles.

[0004] It should be noted that the above content is not necessarily prior art, nor is it intended to limit the scope of patent protection of this application. Summary of the Invention

[0005] This application provides hole transport layers and their preparation methods, solar cells and their preparation methods, and photovoltaic modules to solve or alleviate the technical problem mentioned above where poor uniformity exists during the large-area preparation of hole transport layers, affecting the photoelectric performance and stability of the battery devices.

[0006] The first aspect of this application provides a hole transport layer comprising a carbazole phosphate derivative containing a triazole ring.

[0007] The hole transport layer provided in this application includes a carbazole phosphate derivative containing a triazole ring, which gives the hole transport layer good uniformity and can effectively passivate substrate defects, reducing leakage current problems; it can also avoid the moisture absorption problem when small molecules are used directly, improving the stability of the hole transport layer and extending the device lifespan.

[0008] Optionally, the general structural formula of the triazole ring-containing carbazole phosphate derivative is shown in (1) below: (1) Where A is or B represents a carbazole group; n1 and n2 are the same or different integers from 1 to 12.

[0009] The phosphate group contained in A provided in this application embodiment can serve as an anchoring group, which can enhance the strong interaction with the substrate and improve the coverage effect and defect passivation effect on the substrate.

[0010] Optionally, the Ar in the group is at least one of phenyl, thiophene, naphthyl, furanyl, biphenyl or pyridine.

[0011] Optionally, the carbazole-containing group includes any one of the following B01 to B04:

[0012] R1 and R2 are independently selected from at least one of hydrogen, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, methoxy, phenyl, thiophene, furan, or benzophenyl.

[0013] The carbazole-containing groups provided in this application contain specific R1 and R2 groups, which can regulate the molecular energy level, achieve energy level matching with the perovskite light-absorbing layer, optimize the electron transport characteristics of the molecule, improve hole extraction efficiency, and enhance the hydrophobicity of the molecule, reducing the moisture absorption effect generated when preparing a large-area hole transport layer.

[0014] A second aspect of this application provides a method for preparing a hole transport layer, comprising the following steps: A phosphoric acid compound containing an azide group and a carbazole derivative containing an alkynyl group are reacted via a click reaction to generate a carbazole phosphate derivative containing a triazole ring; the structural formula of the phosphoric acid compound containing the azide group is shown below: ,

[0015] Where n is 1-12; Ar is at least one of phenyl, thiophene, naphthyl, furanyl, biphenyl, or pyridine.

[0016] The hole transport layer preparation method provided in this application includes a click reaction between a phosphate compound with an azide group and a carbazole derivative containing an alkyne group to generate a carbazole phosphate derivative containing a triazole ring, thereby forming a hole transport layer. The reaction between the phosphate compound with the azide group and the carbazole derivative containing the alkyne group achieves precise assembly of the hole transport layer, improves the uniformity of large-area hole transport layer preparation, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption problems associated with direct use of small molecules, improves the stability of the hole transport layer, and extends device lifespan.

[0017] Optionally, the alkynyl-containing carbazole derivative is selected from the following structures:

[0018] R1 and R2 are independently selected from at least one of hydrogen, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, methoxy, phenyl, thiophene, furan, or benzophenyl.

[0019] The carbazole derivative containing alkynyl groups provided in this application contains specific R1 and R2 groups, which can regulate the molecular energy level to achieve energy level matching with the perovskite light-absorbing layer. It can also optimize the electron transport characteristics of the molecule, improve the hole extraction efficiency, and enhance the hydrophobicity of the molecule, reducing the moisture absorption effect generated when preparing a large-area hole transport layer.

[0020] Optionally, the method for preparing the hole transport layer includes the following steps: Monolayer A was prepared using a phosphoric acid compound with an azide group; A small molecule layer B is prepared on the surface of the monolayer A using a carbazole derivative containing an alkyne group, and a triazole ring-containing carbazole derivative is generated between the phosphoric acid compound with an azide group and the carbazole derivative containing an alkyne group through a click reaction, thereby forming a hole transport layer.

[0021] The hole transport layer preparation method provided in this application includes a click reaction between a phosphate compound with an azide group and a carbazole derivative containing an alkyne group to generate a carbazole phosphate derivative containing a triazole ring, thereby forming a hole transport layer. The reaction between the phosphate compound with the azide group and the carbazole derivative containing the alkyne group achieves precise assembly of the hole transport layer, improves the uniformity of large-area hole transport layer preparation, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption problems associated with direct use of small molecules, improves the stability of the hole transport layer, and extends device lifespan.

[0022] Optionally, a hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL is prepared by a phosphoric acid compound containing an azide group. The hole transport precursor solution A is placed on a conductive substrate for film formation, and a monolayer A is obtained after annealing.

[0023] In this embodiment, a hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL is prepared by a phosphoric acid compound containing azide groups. The hole transport precursor solution A is placed on a conductive substrate for film formation. After annealing, a monolayer A is obtained. This process ensures that the phosphoric acid compound containing azide groups is uniformly adsorbed on the substrate surface to form a dense monolayer. Furthermore, the annealing process enhances the binding force between the molecules and the substrate, effectively passivating substrate defects.

[0024] Optionally, a hole transport precursor solution B with a mass-volume concentration of 0.05-5 mg / mL is prepared by preparing a carbazole derivative containing an alkyne group. The hole transport precursor solution B is placed on a monolayer A for film formation treatment. The click reaction is carried out by annealing to generate a carbazole phosphate derivative containing a triazole ring, thus forming a hole transport layer.

[0025] In this embodiment, a hole transport precursor solution B with a mass-volume concentration of 0.05-5 mg / mL is prepared from a carbazole derivative containing an alkyne group. This solution B is then placed on a monolayer A for film formation. An annealing process induces a click reaction to generate a carbazole phosphate derivative containing a triazole ring, forming a hole transport layer. This process ensures that the hole transport precursor solution B uniformly covers the surface of monolayer A, preventing localized aggregation. The annealing process further promotes the reaction between the phosphate compound with an azide group and the carbazole derivative containing the alkyne group, resulting in a carbazole phosphate derivative containing a triazole ring and a structurally stable hole transport layer, thus improving the performance stability of the solar cell device.

[0026] A third aspect of this application provides a solar cell, including a hole transport layer as described in the embodiments of this application or a hole transport layer prepared by the method described in the embodiments of this application.

[0027] The solar cells provided in this application include a hole transport layer as described in the embodiments of this application or a hole transport layer prepared by the method described in the embodiments of this application. This can solve the uniformity problem in the large-area preparation of solar cells, improve the photoelectric conversion efficiency of solar cells, enhance the environmental stability of solar cells, and extend the service life of solar cells.

[0028] Optionally, the solar cell includes a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and an electrode layer, wherein the conductive substrate, the hole transport layer, the perovskite light-absorbing layer, the electron transport layer, and the electrode layer are stacked sequentially.

[0029] Optionally, the solar cell includes a perovskite solar cell, which may include a single-junction perovskite solar cell or a tandem perovskite solar cell.

[0030] The solar cells provided in this application include perovskite solar cells, which can solve the uniformity problem in the large-area fabrication of perovskite solar cells, improve the photoelectric conversion efficiency of perovskite solar cells, enhance the environmental stability of perovskite solar cells, and extend their service life.

[0031] The fourth aspect of this application provides a method for preparing a solar cell, comprising the following steps: A hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL was prepared by a phosphoric acid compound containing an azide group. The hole transport precursor solution A was placed on a conductive substrate for film formation, and a monolayer A was obtained after annealing. A hole transport precursor solution B with a mass-volume concentration of 0.05-5 mg / mL was prepared by preparing a carbazole derivative containing an alkyne group. The hole transport precursor solution B was placed on a monolayer A for film formation treatment. The click reaction was carried out by annealing to generate a carbazole phosphate derivative containing a triazole ring, thus forming a hole transport layer. A perovskite light-absorbing layer is formed on the hole transport layer. An electron transport layer is formed on the perovskite light-absorbing layer; An electrode layer is formed on the electron transport layer.

[0032] This application provides a method for fabricating solar cells, which improves the uniformity of large-area hole transport layer fabrication, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption issues when small molecules are used directly, achieves molecular energy level matching, effectively extracts charge carriers from perovskite, improves efficiency, enhances the stability of the hole transport layer, and extends the lifespan of solar cell devices. The fabrication method provided in this application simplifies the solar cell fabrication process, reduces process complexity, and ensures good interfacial bonding between the hole transport layer, conductive substrate, and perovskite light-absorbing layer, making it suitable for large-area mass production and further reducing manufacturing costs.

[0033] The fifth aspect of this application provides a photovoltaic module, including a solar cell as described in the embodiments of this application, or a solar cell prepared by the method described in the embodiments of this application.

[0034] The photovoltaic modules provided in this application include solar cells as described in this application, or solar cells prepared by the method described in this application. These modules can improve the overall photoelectric conversion efficiency and power output of the photovoltaic modules, enhance the long-term outdoor stability of the modules, and extend their service life.

[0035] The embodiments of this application employing the above-described technical solution may have the following advantages: The hole transport layer provided in this application includes a carbazole phosphate derivative containing a triazole ring, which gives the hole transport layer good uniformity and can effectively passivate substrate defects, reducing leakage current problems; it can also avoid the moisture absorption problem when small molecules are used directly, improving the stability of the hole transport layer and extending the device lifespan.

[0036] The hole transport layer preparation method provided in this application includes a click reaction between a phosphate compound with an azide group and a carbazole derivative containing an alkyne group to generate a carbazole phosphate derivative containing a triazole ring, thereby forming a hole transport layer. The reaction between the phosphate compound with the azide group and the carbazole derivative containing the alkyne group achieves precise assembly of the hole transport layer, improves the uniformity of large-area hole transport layer preparation, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption problems associated with direct use of small molecules, improves the stability of the hole transport layer, and extends device lifespan.

[0037] The solar cells provided in this application include a hole transport layer as described in the embodiments of this application or a hole transport layer prepared by the method described in the embodiments of this application. This can solve the uniformity problem in the large-area preparation of solar cells, improve the photoelectric conversion efficiency of solar cells, enhance the environmental stability of solar cells, and extend the service life of solar cells.

[0038] This application provides a method for fabricating solar cells, which improves the uniformity of large-area hole transport layer fabrication, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption issues when small molecules are used directly, achieves molecular energy level matching, effectively extracts charge carriers from perovskite, improves efficiency, enhances the stability of the hole transport layer, and extends the lifespan of solar cell devices. The fabrication method provided in this application simplifies the solar cell fabrication process, reduces process complexity, and ensures good interfacial bonding between the hole transport layer, conductive substrate, and perovskite light-absorbing layer, making it suitable for large-area mass production and further reducing manufacturing costs.

[0039] The photovoltaic modules provided in this application include solar cells as described in this application, or solar cells prepared by the method described in this application. These modules can improve the overall photoelectric conversion efficiency and power output of the photovoltaic modules, enhance the long-term outdoor stability of the modules, and extend their service life. Attached Figure Description

[0040] In the accompanying drawings, unless otherwise specified, the same reference numerals throughout the various drawings denote the same or similar parts or elements. These drawings are not necessarily drawn to scale. It should be understood that these drawings depict only some embodiments disclosed in this application and should not be construed as limiting the scope of this application.

[0041] Figure 1 This is a schematic diagram of the structure of the perovskite solar cell provided in Embodiment 1 of this application.

[0042] Explanation of reference numerals in the attached figures: Figure 1 In the middle: conductive substrate 100, hole transport layer 200, perovskite light-absorbing layer 300, electron transport layer 400, hole blocking layer 500, electrode layer 600. Detailed Implementation

[0043] The embodiments of this application are described in detail below, examples of which are illustrated in the accompanying drawings. In the drawings, for clarity, the dimensions of layers, regions, and elements, as well as their relative dimensions, may be exaggerated. Throughout, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application. It should be noted that, unless otherwise specified, the features of this application and its embodiments can be combined with each other.

[0044] It should be understood that when an element or layer is referred to as "on," "adjacent to," "connected to," or "coupled to" other elements or layers, it may be directly on, adjacent to, connected to, or coupled to other elements or layers, or there may be intervening elements or layers. Conversely, when an element is referred to as "directly on," "directly adjacent to," "directly connected to," or "directly coupled to" other elements or layers, there are no intervening elements or layers. It should be understood that although the terms first, second, third, etc., may be used to describe various elements, components, areas, layers, and / or portions, these elements, components, areas, layers, and / or portions should not be limited by these terms. These terms are only used to distinguish one element, component, area, layer, or portion from another element, component, area, layer, or portion. Therefore, without departing from the teachings of this application, the first element, component, area, layer, or portion discussed below may be referred to as a second element, component, area, layer, or portion. And the discussion of a second element, component, area, layer, or portion does not imply that the first element, component, area, layer, or portion necessarily exists in this application.

[0045] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "joining," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise expressly limited. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0046] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this application are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such terms can be used interchangeably where appropriate so that the embodiments of this application described herein can be implemented, for example, in orders other than those illustrated or described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover a non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0047] This application involves numerical intervals (i.e., numerical ranges). Unless otherwise specified, the distribution of selectable numerical values ​​within a numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, etc.

[0048] Exemplary embodiments according to this application will now be described in more detail with reference to the accompanying drawings. It should be understood that these exemplary embodiments may be implemented in many different forms and should not be construed as being limited to the embodiments set forth herein.

[0049] This application provides a hole transport layer comprising a carbazole phosphate derivative containing a triazole ring.

[0050] The hole transport layer provided in this application includes a carbazole phosphate derivative containing a triazole ring, which gives the hole transport layer good uniformity and can effectively passivate substrate defects, reducing leakage current problems; it can also avoid the moisture absorption problem when small molecules are used directly, improving the stability of the hole transport layer and extending the device lifespan.

[0051] In an optional embodiment, the general structural formula of the triazole ring-containing carbazole phosphate derivative is shown below (1): (1) Where A is or B is a carbazole group; n1 and n2 are the same or different integers from 1 to 12 (for example, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12).

[0052] The phosphate group contained in A provided in this application embodiment can serve as an anchoring group, which can enhance the strong interaction with the substrate and improve the coverage effect and defect passivation effect on the substrate.

[0053] In an optional embodiment, the Ar in the group is at least one of phenyl, thiophene, naphthyl, furanyl, biphenyl or pyridine.

[0054] In an optional embodiment, the carbazole-containing group includes any one of the following B01 to B04:

[0055] R1 and R2 are independently selected from at least one of hydrogen, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, methoxy, phenyl, thiophene, furan, or benzophenyl.

[0056] In an optional embodiment, the structural formulas of B01 to B04 are not methyl groups, but rather carbon chain saturated bonds with alkynyl groups attached thereto.

[0057] The carbazole-containing groups provided in this application contain specific R1 and R2 groups, which can regulate the molecular energy level, achieve energy level matching with the perovskite light-absorbing layer, optimize the electron transport characteristics of the molecule, improve hole extraction efficiency, and enhance the hydrophobicity of the molecule, reducing the moisture absorption effect generated when preparing a large-area hole transport layer.

[0058] This application provides a method for preparing a hole transport layer, including the following steps: A phosphoric acid compound containing an azide group and a carbazole derivative containing an alkynyl group are reacted via a click reaction to generate a carbazole phosphate derivative containing a triazole ring; the structural formula of the phosphoric acid compound containing the azide group is shown below: ,

[0059] Where n is 1-12 (for example, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12); Ar is at least one of phenyl, thiophene, naphthyl, furanyl, biphenyl, or pyridine.

[0060] The phosphate groups in the phosphate compounds with azide groups provided in this application can act as anchoring groups, enhancing strong interactions with the substrate and improving the coverage and defect passivation effects on the substrate.

[0061] The azido group in the phosphate compound containing an azido group provided in this application undergoes a click reaction with the alkynyl group in the carbazole derivative containing an alkynyl group to generate a triazole ring group, thereby obtaining a carbazole phosphate derivative containing a triazole ring. The hole transport layer preparation method provided in this application includes a click reaction between a phosphate compound with an azide group and a carbazole derivative containing an alkyne group to generate a carbazole phosphate derivative containing a triazole ring, thereby forming a hole transport layer. The reaction between the phosphate compound with the azide group and the carbazole derivative containing the alkyne group achieves precise assembly of the hole transport layer, improves the uniformity of large-area hole transport layer preparation, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption problems associated with direct use of small molecules, improves the stability of the hole transport layer, and extends device lifespan.

[0062] In an optional embodiment, the phosphate compound containing an azide group is selected from the following structures:

[0063] In an optional embodiment, the alkynyl-containing carbazole derivative is selected from the following structures:

[0064] R1 and R2 are independently selected from at least one of hydrogen, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, methoxy, phenyl, thiophene, furan, or benzophenyl.

[0065] In an optional embodiment, R1 and R2 are hydrogen.

[0066] The carbazole derivative containing alkynyl groups provided in this application contains specific R1 and R2 groups, which can regulate the molecular energy level to achieve energy level matching with the perovskite light-absorbing layer. It can also optimize the electron transport characteristics of the molecule, improve the hole extraction efficiency, and enhance the hydrophobicity of the molecule, reducing the moisture absorption effect generated when preparing a large-area hole transport layer.

[0067] In an optional embodiment, the alkynyl-containing carbazole derivative is selected from the following structures:

[0068] In an optional embodiment, the method for preparing the hole transport layer includes the following steps: Monolayer A was prepared using a phosphoric acid compound with an azide group; A small molecule layer B is prepared on the surface of the monolayer A using a carbazole derivative containing an alkyne group, and a triazole ring-containing carbazole derivative is generated between the phosphoric acid compound with an azide group and the carbazole derivative containing an alkyne group through a click reaction, thereby forming a hole transport layer.

[0069] The hole transport layer preparation method provided in this application includes a click reaction between a phosphate compound with an azide group and a carbazole derivative containing an alkyne group to generate a carbazole phosphate derivative containing a triazole ring, thereby forming a hole transport layer. The reaction between the phosphate compound with the azide group and the carbazole derivative containing the alkyne group achieves precise assembly of the hole transport layer, improves the uniformity of large-area hole transport layer preparation, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption problems associated with direct use of small molecules, improves the stability of the hole transport layer, and extends device lifespan.

[0070] In an optional embodiment, a phosphoric acid compound with an azide group is prepared into a hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations such as 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL, etc.). The hole transport precursor solution A is placed on a conductive substrate for film formation, and a monolayer A is obtained after annealing.

[0071] In this embodiment, a hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL is prepared by a phosphoric acid compound containing azide groups. The hole transport precursor solution A is placed on a conductive substrate for film formation. After annealing, a monolayer A is obtained. This process ensures that the phosphoric acid compound containing azide groups is uniformly adsorbed on the substrate surface to form a dense monolayer. Furthermore, the annealing process enhances the binding force between the molecules and the substrate, effectively passivating substrate defects.

[0072] In an optional embodiment, a carbazole derivative containing an alkyne group is prepared into a hole transport precursor solution B with a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations include 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL, etc.). The hole transport precursor solution B is placed on a monolayer A for film formation treatment. An annealing treatment is then performed to induce a click reaction to generate a carbazole phosphate derivative containing a triazole ring, thus forming a hole transport layer.

[0073] In this embodiment, a hole transport precursor solution B with a mass-volume concentration of 0.05-5 mg / mL is prepared from a carbazole derivative containing an alkyne group. This solution B is then placed on a monolayer A for film formation. An annealing process induces a click reaction to generate a carbazole phosphate derivative containing a triazole ring, forming a hole transport layer. This process ensures that the hole transport precursor solution B uniformly covers the surface of monolayer A, preventing localized aggregation. The annealing process further promotes the reaction between the phosphate compound with an azide group and the carbazole derivative containing the alkyne group, resulting in a carbazole phosphate derivative containing a triazole ring and a structurally stable hole transport layer, thus improving the performance stability of the solar cell device.

[0074] This application provides a solar cell, including a hole transport layer as described in this application or a hole transport layer prepared by the method described in this application.

[0075] The solar cells provided in this application include a hole transport layer as described in the embodiments of this application or a hole transport layer prepared by the method described in the embodiments of this application. This can solve the uniformity problem in the large-area preparation of solar cells, improve the photoelectric conversion efficiency of solar cells, enhance the environmental stability of solar cells, and extend the service life of solar cells.

[0076] In an optional embodiment, the solar cell includes a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and an electrode layer, wherein the conductive substrate, the hole transport layer, the perovskite light-absorbing layer, the electron transport layer, and the electrode layer are stacked sequentially.

[0077] In an optional embodiment, the solar cell includes a perovskite solar cell, which includes a single-junction perovskite solar cell or a tandem perovskite solar cell.

[0078] The solar cells provided in this application include perovskite solar cells, which can solve the uniformity problem in the large-area fabrication of perovskite solar cells, improve the photoelectric conversion efficiency of perovskite solar cells, enhance the environmental stability of perovskite solar cells, and extend their service life.

[0079] This application provides a method for preparing a solar cell, comprising the following steps: A hole transport precursor solution A is prepared by preparing a phosphoric acid compound with an azide group into a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations include 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL, etc.). The hole transport precursor solution A is placed on a conductive substrate for film formation, and a monolayer A is obtained after annealing. A hole transport precursor solution B is prepared by preparing a carbazole derivative containing an alkyne group with a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations include 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL, etc.). The hole transport precursor solution B is placed on a monolayer A for film formation treatment. The click reaction occurs through annealing to generate a carbazole phosphate derivative containing a triazole ring, thus forming a hole transport layer. A perovskite light-absorbing layer is formed on the hole transport layer. An electron transport layer is formed on the perovskite light-absorbing layer; An electrode layer is formed on the electron transport layer.

[0080] This application provides a method for fabricating solar cells, which improves the uniformity of large-area hole transport layer fabrication, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption issues when small molecules are used directly, achieves molecular energy level matching, effectively extracts charge carriers from perovskite, improves efficiency, enhances the stability of the hole transport layer, and extends the lifespan of solar cell devices. The fabrication method provided in this application simplifies the solar cell fabrication process, reduces process complexity, and ensures good interfacial bonding between the hole transport layer, conductive substrate, and perovskite light-absorbing layer, making it suitable for large-area mass production and further reducing manufacturing costs.

[0081] In an optional embodiment, the method for preparing the solar cell includes the following steps: S1. Clean and dry the conductive substrate for later use. Place the dried conductive substrate in an ultraviolet ozone machine for treatment to remove organic impurities on the surface of the conductive substrate and optimize the wettability of the conductive substrate surface. S2. Prepare a hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations include 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL, etc.) by preparing a phosphoric acid compound containing an azide group. Place the hole transport precursor solution A on a conductive substrate for film formation. After annealing, obtain a monomolecular... Layer A: Prepare a hole transport precursor solution B with a carbazole derivative containing an alkyne group at a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations include 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL, etc.). Place the hole transport precursor solution B on monolayer A for film formation treatment, and obtain the hole transport layer through click reaction. S3. Add the material of the perovskite light-absorbing layer to the solvent and stir at room temperature until completely dissolved to obtain a perovskite precursor solution; in a nitrogen glove box, take the perovskite precursor solution and drop it onto the conductive substrate to form the hole transport layer, and perform spin coating to form a film. During the spin coating process, add chlorobenzene and place the conductive substrate on a hot plate for heating and annealing to form a perovskite light-absorbing layer. S4. Add the electron transport layer material to the solvent and stir at room temperature (25°C) until dissolved to obtain an electron transport layer material solution; take 20-50 μL (exemplary values ​​such as 20 μL, 25 μL, 30 μL, 35 μL, 40 μL, 45 μL, 50 μL, etc.) of the electron transport layer material solution and drop it onto the perovskite light-absorbing layer, and perform spin-coating to form an electron transport layer; S5. Add the hole blocking layer material to the solvent and stir at room temperature (25°C) until dissolved to obtain a hole blocking layer solution; take 20-50 μL (exemplary values ​​such as 20 μL, 25 μL, 30 μL, 35 μL, 40 μL, 45 μL, 50 μL, etc.) of the hole blocking layer solution and drop it onto the electron transport layer, and perform spin coating to form a hole blocking layer; S6. Transfer the TCO conductive glass, to which the hole transport layer, perovskite light-absorbing layer, electron transport layer, and hole blocking layer are sequentially formed, to a vacuum coating instrument, and wait for the vacuum level to reach 1-5×10⁻⁶. -4 Pa (for example, such as 1×10) -4 Pa, 2×10 - 4Pa, 3×10 -4 Pa, 4×10 -4 Pa, 5×10 -4 Electrode materials are vapor-deposited at Pa (e.g.) to form an electrode layer on a hole-blocking layer.

[0082] The conductive substrate in S1 includes TCO conductive glass.

[0083] The perovskite light-absorbing layer in S3 comprises a first perovskite material and a second perovskite material. The first perovskite material is selected from at least one of lead halide and tin halide; the second perovskite material is selected from at least one of formamidinium halide, methylamine halide and cesium halide.

[0084] The lead halide salts include lead iodide.

[0085] The methylamine halide salts include iodomethylamine.

[0086] The electron transport layer material in S4 is selected from at least one of methane fullerene phenyl-C61-butyrate methyl ester, C60, or tin oxide.

[0087] The hole-blocking layer in S5 is made of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline or zirconium acetylacetonate.

[0088] The electrode material in S6 is selected from at least one of silver, copper, conductive oxide, or carbon.

[0089] In an optional embodiment, the method for preparing the solar cell includes the following steps: S1. The TCO conductive glass is ultrasonically cleaned sequentially with deionized water, acetone, and isopropanol for 10-20 minutes each (exemplary, such as 10 minutes, 15 minutes, 20 minutes, etc.). After cleaning, it is placed in a drying oven at 70-80℃ (exemplary, such as 70℃, 75℃, 80℃, etc.) for drying. The dried TCO conductive glass is then placed in an ultraviolet ozone generator for 20-30 minutes (exemplary, such as 20 minutes, 25 minutes, 30 minutes, etc.) to remove organic impurities from the surface of the TCO conductive glass and optimize the surface wettability of the TCO conductive glass. S2. The phosphoric acid compound containing an azide group is added to ethanol and stirred to dissolve, obtaining a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations include 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL). Hole transport precursor solution A (e.g., 0.05 mg / mL); A carbazole derivative containing an alkyne group is added to ethanol and stirred to dissolve, obtaining a mass-volume concentration of 0.05-5 mg / mL (exemplary concentrations include 0.05 mg / mL, 0.1 mg / mL, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4 mg / mL).Hole transport precursor solution B (5 mg / mL, 5 mg / mL, etc.) is prepared. Micelles with a particle size greater than or equal to 500 nm in hole transport precursor solution A are removed by filtration before being dropped onto TCO conductive glass. Spin-coating is then performed at 4500-5500 rpm (exemplary speeds such as 4500 rpm, 5000 rpm, 5500 rpm, etc.) for 20-40 seconds (exemplary speeds such as 20 s, 25 s, 30 s, 35 s, 40 s, etc.). After spin-coating, the TCO conductive glass is placed on a hot stage. Heating and annealing at 30-150℃ (exemplary values ​​such as 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, etc.) for 1-60 minutes (exemplary values ​​such as 1 minute, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, etc.) is performed to achieve TCO conduction. A small molecular layer A is formed on the conductive glass. Micelles with a particle size greater than or equal to 500 nm in the hole transport precursor solution B are removed by filtration and then dropped onto the small molecular layer A obtained on the TCO conductive glass. Spin-coating is then performed at a speed of 4500-5500 rpm (exemplary speeds such as 4500 rpm, 5000 rpm, 5500 rpm, etc.) for 20-40 seconds (exemplary speeds such as 20 s, 25 s, 30 s, 35 s, 40 s, etc.). After spin-coating, the TCO conductive glass is placed on a hot plate and heated for 30-15 seconds. A hole transport layer with a thickness of 0.5-10 nm (exemplary values ​​such as 0.5 nm, 1 nm, 3 nm, 10 nm, 40 nm, 50 nm, 60 nm, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, etc.) is formed by heating and annealing at 50 °C (exemplary values ​​such as 30 °C, 40 °C, 50 °C, 10 °C, etc.) for 1-60 min (exemplary values ​​such as 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, etc.). The solvents used in the embodiments of this application to dissolve phosphoric acid compounds containing azide groups include, but are not limited to, ethanol. Any solvent that can achieve the dissolution effect is acceptable. The use of ethanol to dissolve phosphoric acid compounds containing azide groups does not limit the scope of protection. The solvents used in the embodiments of this application to dissolve carbazole derivatives containing alkynyl groups include, but are not limited to, ethanol. Any solvent that can achieve the dissolution effect is acceptable. The use of ethanol to dissolve carbazole derivatives containing alkynyl groups does not limit the scope of protection. S3. Add 720-725 mg (exemplary, such as 720 mg, 720.5 mg, 721 mg, 721.5 mg, 722 mg, 722.5 mg, 723 mg, 723.5 mg, 724 mg, 724.5 mg, 725 mg, etc.) of lead iodide and 235-240 mg (exemplary, such as 235 mg, 235.5 mg, 236 mg, 236.5 mg, 237 mg, 237.5 mg, 238 mg, 238.5 mg, 239 mg, 239.5 mg, 240 mg, etc.) of methyl iodide to 0.5-5 mL (exemplary, ... Dissolve perovskite precursor solutions in N,N-dimethylformamide (DMF) in amounts such as 0.5 mL, 1 mL, 2 mL, 3 mL, 4 mL, 5 mL, etc., and stir at room temperature (25°C) until completely dissolved to obtain a perovskite precursor solution. In a nitrogen glove box, add 20-40 μL (exemplary values ​​such as 20 μL, 30 μL, 40 μL, etc.) of the perovskite precursor solution dropwise onto the hole transport layer formed by the TCO conductive glass. Spin-coat the solution at 800-2000 rpm (exemplary values ​​such as 800 rpm, 1000 rpm, 1500 rpm, 2000 rpm, etc.) for 5-15 seconds (exemplary values ​​such as 5...). (e.g., 10s, 15s, etc.), then spin-coat at 4500-5500 rpm (e.g., 4500 rpm, 5000 rpm, 5500 rpm, etc.) for 20-40s (e.g., 20s, 25s, 30s, 35s, 40s, etc.). During the spin-coating process, at the 20-30s mark (e.g., 20s, 25s, 30s, etc.), drop 100-150 μL (e.g., 100μL, 105μL, 110μL, 115μL, 120μL, 125μL, 130μL, 135μL, 140μL, 1...) within 1 second. Chlorobenzene (45 μL, 150 μL, etc.) is added, and then the TCO conductive glass is placed on a hot stage and annealed at 90-130℃ (exemplary, such as 90℃, 100℃, 110℃, 120℃, 130℃, etc.) for 20-60 min (exemplary, such as 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, etc.) to form a perovskite light-absorbing layer with a thickness of 300-800 nm (exemplary, such as 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, etc.). S4. Add 10-30 mg (exemplary, such as 10 mg, 20 mg, 30 mg, etc.) of electron transport layer material to 0.5-5 mL (exemplary, such as 0.5 mL, 1 mL, 2 mL, 3 mL, 4 mL, 5 mL, etc.) of chlorobenzene, and stir at room temperature (25°C) until dissolved to obtain an electron transport layer material solution; take 20-50 μL (exemplary, such as 20 μL, 25 μL, 30 μL, 35 μL, 40 μL, 45 μL, 50 μL, etc.) of the electron transport layer material solution and drop it onto the perovskite light-absorbing layer. Spin-coating is performed at a rotation speed of 2000-4000 rpm (exemplary, such as 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, etc.) for 40-80 s (exemplary, such as 40 s, 45 s, 50 s, 55 s, 60 s, 65 s, 70 s, 75 s, 80 s, etc.) to form an electron transport layer with a thickness of 10-80 nm (exemplary, such as 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, etc.). S5. Add 0.1-5 mg (exemplary, such as 0.1 mg, 0.5 mg, 1 mg, 2 mg, 3 mg, 4 mg, 5 mg, etc.) of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) or zirconium acetylacetonate to 0.5-5 mL (exemplary, such as 0.5 mL, 1 mL, 2 mL, 3 mL, 4 mL, 5 mL, etc.) of isopropanol and stir at room temperature (25°C) until dissolved to obtain a hole-blocking layer solution; take 20-50 μL (exemplary, such as 20 μL, 25 μL, 30 μL, 3... Hole blocking layer solutions of 5 μL, 40 μL, 45 μL, 50 μL, etc. are dropped onto the electron transport layer and spin-coated for 20-50 s (exemplary, such as 4500 rpm, 5000 rpm, 5500 rpm, etc.) at a rotation speed of 4500-5500 rpm (exemplary, such as 20 s, 25 s, 30 s, 35 s, 40 s, 45 s, 50 s, etc.) to form a hole blocking layer with a thickness of 1-20 nm (exemplary, such as 1 nm, 3 nm, 6 nm, 9 nm, 12 nm, 15 nm, 18 nm, 20 nm, etc.). S6. Transfer the TCO conductive glass, to which the hole transport layer, perovskite light-absorbing layer, electron transport layer, and hole blocking layer are sequentially formed, to a vacuum coating instrument, and wait for the vacuum level to reach 1-5×10⁻⁶. -4 Pa (for example, such as 1×10) -4 Pa, 2×10 - 4 Pa, 3×10 -4 Pa, 4×10 -4 Pa, 5×10 -4Electrode materials are vapor-deposited at a pressure of Pa (e.g., Pa), forming an electrode layer with a thickness of 50-200 nm (exemplary thicknesses such as 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 180 nm, 200 nm, etc.) on a hole blocking layer.

[0090] The electron transport layer material in S4 is selected from at least one of methane fullerene phenyl-C61-butyrate methyl ester, C60, or tin oxide.

[0091] The electrode material in S6 is selected from at least one of silver, copper, conductive oxide, or carbon.

[0092] This application provides a photovoltaic module, including a solar cell as described in this application embodiment, or a solar cell prepared by the method described in this application embodiment.

[0093] The following section will conduct performance tests on the structure or fabrication method of the solar cell provided in the embodiments of this application, as well as related comparative examples.

[0094]

Example 1

[0095] This application provides a method for fabricating a perovskite solar cell, comprising the following steps: S1. TCO conductive glass is used as a conductive substrate and ultrasonically cleaned with deionized water, acetone and isopropanol for 15 min each. After cleaning, it is placed in a drying oven at 75℃ for drying. The dried TCO conductive glass is placed in an ultraviolet ozone machine for 25 min to remove organic impurities on the surface of TCO conductive glass and optimize the surface wettability of TCO conductive glass. S2. A phosphoric acid compound A1 containing an azide group is added to ethanol and stirred to dissolve, obtaining a hole transport precursor solution A with a mass-volume concentration of 0.5 mg / mL; a carbazole derivative B1 containing an alkyne group is added to ethanol and stirred to dissolve, obtaining a hole transport precursor solution B with a mass-volume concentration of 0.5 mg / mL; after removing micelles with a particle size greater than or equal to 500 nm from hole transport precursor solution A by filtration, hole transport precursor solution A is dropped onto a TCO conductive glass substrate and then rotated at 5000 rpm. Spin-coating for 30 seconds, and after spin-coating, the TCO conductive glass is placed on a hot stage and annealed at 100°C for 10 minutes to form a small molecular layer A on the TCO conductive glass. After removing micelles with a particle size greater than or equal to 500 nm from the hole transport precursor solution B by filtration, the hole transport precursor solution is dropped onto the small molecular layer A obtained on the TCO conductive glass, and then spin-coated at 5000 rpm for 30 seconds. After spin-coating, the TCO conductive glass is placed on a hot stage and annealed at 100°C for 10 minutes to form a hole transport layer with a thickness of 1 nm. S3. Add 722.08 mg lead iodide and 238.50 mg methyl iodide to 1 mL of N,N-dimethylformamide (DMF) and stir at room temperature (25 °C) until completely dissolved to obtain a perovskite precursor solution. In a nitrogen glove box, take 30 μL of the perovskite precursor solution and drop it onto the hole transport layer formed by TCO conductive glass. First, spin coat at 1000 rpm for 10 s, then spin coat at 5000 rpm for 30 s. During the spin coating process, when spin coating reaches 25 s, add 125 μL of chlorobenzene within 1 s. Then place the TCO conductive glass on a hot stage and heat it at 100 °C for annealing for 40 min to form a perovskite light-absorbing layer with a thickness of 500 nm. S4. Add 20 mg of methyl methane fullerene phenyl-C61-butyrate (PCBM) to 1 mL of chlorobenzene and stir at room temperature (25 °C) until dissolved to obtain a methyl methane fullerene phenyl-C61-butyrate solution; take 30 μL of the methyl methane fullerene phenyl-C61-butyrate solution and drop it onto the perovskite light-absorbing layer, spin-coat at 3000 rpm for 60 s to form an electron transport layer with a thickness of 30 nm; S5. Add 0.5 mg of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) to 1 mL of isopropanol and stir at room temperature (25 °C) until dissolved to obtain a hole blocking layer solution; take 40 μL of the hole blocking layer solution and drop it onto the electron transport layer, spin-coat at 5000 rpm for 35 s to form a hole blocking layer with a thickness of 6 nm; S6. Transfer the TCO conductive glass, to which the hole transport layer, perovskite light-absorbing layer, electron transport layer, and hole blocking layer are sequentially formed, to a vacuum coating instrument, and wait for the vacuum level to reach 3×10⁻⁶. -4 Silver is deposited by vapor deposition at Pa to form a silver electrode with a thickness of 100 nm on the hole blocking layer, thus obtaining the electrode layer.

[0096] The structural formula of the phosphate compound A1 with an azide group used in the hole transport precursor solution A in S2 is as follows:

[0097] The hole transport precursor solution B in S2 uses a carbazole derivative B1 containing an alkyne group, with the following structural formula:

[0098]

Example 2

[0099] The structural formula of the phosphate compound A1 with an azide group used in the hole transport precursor solution A in S2 is as follows:

[0100] The hole transport precursor solution B in S2 uses a carbazole derivative B2 containing an alkyne group, with the following structural formula:

[0101]

Example 3

[0102] The structural formula of the phosphate compound A1 with an azide group used in the hole transport precursor solution A in S2 is as follows:

[0103] The hole transport precursor solution B in S2 uses a carbazole derivative B3 containing an alkyne group, with the following structural formula:

[0104]

Example 4

[0105] The structural formula of the phosphate compound A1 with an azide group used in the hole transport precursor solution A in S2 is as follows:

[0106] The hole transport precursor solution B in S2 uses a carbazole derivative B4 containing an alkyne group, with the following structural formula:

[0107]

Example 5

[0108] The hole transport precursor solution A in S2 uses a phosphate compound A2 with an azide group, the structural formula of which is:

[0109] The hole transport precursor solution B in S2 uses a carbazole derivative B1 containing an alkyne group, with the following structural formula:

[0110]

Example 6

[0111] The structural formula of the phosphate compound A3 with an azide group used in the hole transport precursor solution A in S2 is as follows:

[0112] The hole transport precursor solution B in S2 uses a carbazole derivative B1 containing an alkyne group, with the following structural formula:

[0113]

Example 7

[0114] The hole transport precursor solution A in S2 uses a phosphate compound A4 with an azide group, which has the following structural formula:

[0115] The hole transport precursor solution B in S2 uses a carbazole derivative B1 containing an alkyne group, with the following structural formula:

[0116] Comparative Example 1 The perovskite solar cell of Comparative Example 1 was prepared according to the fabrication method of the perovskite solar cell provided in Example 1, except that: (4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid (ME-4PACZ) was added to ethanol to prepare a hole transport solution with a mass-volume concentration of 0.5 mg / mL. The hole transport solution was dropped onto TCO conductive glass and then spin-coated at 5000 rpm for 30 s. After spin-coating, the TCO conductive glass was placed on a hot stage and heated and annealed at 100 °C for 10 min to form a hole transport layer with a thickness of 1 nm.

[0117] Performance testing The perovskite solar cells provided in Examples 1-7 and Comparative Example 1 of this application were tested under standard test conditions to obtain the open-circuit voltage Voc, fill factor FF, short-circuit current density Jsc, and photoelectric conversion efficiency PCE of the perovskite solar cells. The test results are shown in Table 1.

[0118] The fill factor (FF) used in this paper refers to the ratio of the actual maximum obtainable power (Pm or Vmp × Jmp) to the theoretical (not actually obtainable) power (Jsc × Voc). Therefore, FF can be determined by the following formula: FF = (Vmp × Jmp) / (Jsc × Voc), Where Jmp and Vmp represent the current density and voltage at the maximum power point (Pm), respectively, which is obtained by changing the resistance in the circuit until J×V reaches its maximum value; Jsc and Voc represent the short-circuit current and open-circuit voltage, respectively. The fill factor is a key parameter for evaluating perovskite solar cells. Commercial perovskite solar cells typically have a fill factor of approximately 60% or higher.

[0119] The open-circuit voltage (Voc) used in this paper is the potential difference between the anode and cathode of the device under conditions of no external load connection.

[0120] The short-circuit current (Isc) used in this article is the maximum current flowing through the output terminal of a photovoltaic cell or module when it is short-circuited (voltage V=0) under STC conditions.

[0121] The power conversion efficiency (PCE) of perovskite solar cells used in this article refers to the percentage of power converted from absorbed light into electrical energy, expressed as a percentage (%). The PCE of perovskite solar cells can be measured under standard test conditions (STC) with incident light irradiance (E: W / m²). 2 ) and the surface area (Ac:m) of perovskite solar cells 2 The STC is calculated by dividing by the point of maximum power (Pm). STC typically refers to the value at a temperature of 25°C and an irradiance of 100 W / m². 2 The spectrum of air quality 1.5 (AM1.5).

[0122] Table 1 provides test data for the perovskite solar cells provided in Examples 1-7 and Comparative Example 1.

[0123] Table 1

[0124] As shown in Table 1 above, the performance of the solar cells provided in Examples 1-7 is superior to that of the solar cell provided in Comparative Example 1. The hole transport layer provided in Examples 1-7 includes a carbazole phosphate derivative containing a triazole ring, which can improve the photoelectric conversion efficiency of the solar cell to 20.15%-22.68%. It can be seen that the use of a carbazole phosphate derivative containing a triazole ring in the embodiments of this application gives the hole transport layer good uniformity, effectively passivates substrate defects, reduces leakage current, avoids moisture absorption problems when small molecules are used directly, and achieves molecular energy level matching, effectively extracting charge carriers from perovskite, thereby improving efficiency, and thus improving the fill factor and short-circuit current of the solar cell; and improving the stability of the hole transport layer, extending the service life of the solar cell device.

[0125] This application embodiment can also provide a photovoltaic module (not shown), which includes the solar cell described above. The solar cell can be connected in series and / or in parallel with one or more other solar cells in a predetermined manner. Multiple cells can form a cell string, and adjacent cells can be connected together by string welding.

[0126] It should be noted that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," etc., are used only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on this application. The directional terms "inner" and "outer" refer to the inside or outside relative to the outline of the component itself. For example, if a device in the drawings is inverted, a device described as "above" or "on top of" other devices or structures will subsequently be positioned as "below" or "under" other devices or structures. Thus, the exemplary term "above" can include both "above" and "below." The device may also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatial relative descriptions used herein are interpreted accordingly.

[0127] It should also be noted that the terms "one embodiment," "another embodiment," and "embodiment" used in this application refer to specific features, structures, or characteristics described in connection with that embodiment, which are included in at least one embodiment described in the general description of this application. The appearance of the same expression in multiple places in the specification does not necessarily refer to the same embodiment. Furthermore, when a specific feature, structure, or characteristic is described in connection with any embodiment, the intention is to suggest that implementing such a feature, structure, or characteristic in conjunction with other embodiments also falls within the scope of this application.

[0128] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0129] It should also be noted that the above are merely preferred embodiments of this application and do not limit the scope of patent protection of this application. Any equivalent structural or procedural changes made using the content of this application’s specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of this application.

Claims

1. A hole transport layer, characterized in that, This includes carbazole phosphate derivatives containing a triazole ring.

2. The hole transport layer according to claim 1, characterized in that, The general structural formula of the triazole ring-containing carbazole phosphate derivative is shown in (1): （1） Where A is or B represents a carbazole group; n1 and n2 are the same or different integers from 1 to 12.

3. The hole transport layer according to claim 1, characterized in that, The Ar in the group is at least one of phenyl, thiophene, naphthyl, furanyl, biphenyl or pyridine.

4. The hole transport layer according to claim 2 or 3, characterized in that, The carbazole-containing group includes any one of the following B01 to B04: R1 and R2 are independently selected from at least one of hydrogen, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, methoxy, phenyl, thiophene, furan, or benzophenyl.

5. A method for preparing a hole transport layer, characterized in that, Includes the following steps: A phosphoric acid compound containing an azide group and a carbazole derivative containing an alkynyl group are reacted via a click reaction to generate a carbazole phosphate derivative containing a triazole ring; the structural formula of the phosphoric acid compound containing the azide group is shown below: 、 Where n is 1-12; Ar is at least one of phenyl, thiophene, naphthyl, furanyl, biphenyl, or pyridine.

6. The method for preparing a hole transport layer according to claim 5, characterized in that, The carbazole derivative containing an alkynyl group is selected from the following structures: R1 and R2 are independently selected from at least one of hydrogen, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, methoxy, phenyl, thiophene, furan, or benzophenyl.

7. The method for preparing a hole transport layer according to claim 5, characterized in that, Includes the following steps: Monolayer A was prepared using a phosphoric acid compound with an azide group; A small molecule layer B is prepared on the surface of the monolayer A using a carbazole derivative containing an alkyne group, and a triazole ring-containing carbazole derivative is generated between the phosphoric acid compound with an azide group and the carbazole derivative containing an alkyne group through a click reaction, thereby forming a hole transport layer.

8. The method for preparing a hole transport layer according to claim 7, characterized in that, A hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL was prepared by a phosphoric acid compound containing an azide group. The hole transport precursor solution A was placed on a conductive substrate for film formation, and a monolayer A was obtained after annealing.

9. The method for preparing a hole transport layer according to claim 8, characterized in that, A hole transport precursor solution B with a mass-volume concentration of 0.05-5 mg / mL was prepared by preparing a carbazole derivative containing an alkyne group. The hole transport precursor solution B was placed on a monolayer A for film formation treatment. The click reaction was carried out by annealing to generate a carbazole phosphate derivative containing a triazole ring, thus forming a hole transport layer.

10. A solar cell comprising a hole transport layer as described in any one of claims 1-4 or a hole transport layer prepared by any one of claims 5-9.

11. The solar cell according to claim 10, characterized in that, The solar cell includes a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, and an electrode layer, wherein the conductive substrate, the hole transport layer, the perovskite light-absorbing layer, the electron transport layer, and the electrode layer are stacked sequentially.

12. The solar cell according to claim 10, characterized in that, The solar cell includes a perovskite solar cell, which includes a single-junction perovskite solar cell or a tandem perovskite solar cell.

13. A method for preparing a solar cell, characterized in that, Includes the following steps: A hole transport precursor solution A with a mass-volume concentration of 0.05-5 mg / mL was prepared by a phosphoric acid compound containing an azide group. The hole transport precursor solution A was placed on a conductive substrate for film formation, and a monolayer A was obtained after annealing. A hole transport precursor solution B with a mass-volume concentration of 0.05-5 mg / mL was prepared by preparing a carbazole derivative containing an alkyne group. The hole transport precursor solution B was placed on a monolayer A for film formation treatment. The click reaction was carried out by annealing to generate a carbazole phosphate derivative containing a triazole ring, thus forming a hole transport layer. A perovskite light-absorbing layer is formed on the hole transport layer. An electron transport layer is formed on the perovskite light-absorbing layer; An electrode layer is formed on the electron transport layer.

14. A photovoltaic module, characterized in that, This includes solar cells as described in any one of claims 10-12, or solar cells prepared by the method described in claim 13.

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