Perovskite solar cell, preparation method thereof and photovoltaic module

Abstract

The invention relates to the technical field of solar cells, in particular to a perovskite solar cell and a preparation method thereof, and a photovoltaic module wherein the perovskite solar cell comprises a substrate structure, and a hole transport layer, a perovskite absorption layer and an electron transport layer which are sequentially stacked on one side of the substrate structure from near to far; the hole transport layer comprises a first material and a second material, and the first material is a phosphonic acid compound containing carbazolyl; and the second material comprises at least one of (4-(pyrene-1-yl) phenyl) phosphonic acid, (4-(6-fluoro-9H-thieno [2, 3,: 4, 5] thieno [3, 2-b] indole-9-yl) butyl) phosphonic acid, (4-(5H-benzo [4, 5] thieno [3, 2-c] indole-9-yl) butyl) phosphonic acid and ((9H-carbazole-3, 6-diyl) bis (4, 1-phenylene)) bisphosphonic acid. According to the technical scheme, the contact uniformity between the hole transport layer and the substrate structure and between the hole transport layer and the perovskite absorption layer in the perovskite solar cell is improved, and the overall electrochemical performance of the perovskite solar cell is effectively improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solar cells, in particular to a perovskite solar cell, a preparation method thereof and a photovoltaic module. BACKGROUND

[0002] In recent years, with the continuous improvement of the photoelectric conversion efficiency of perovskite solar cells, researchers have tried different combinations to improve the theoretical efficiency of perovskite solar cells. At present, at least the following problems exist in perovskite solar cells: The existing hole transport material has poor spreading property and thickness sensitivity, which will cause uneven contact between the substrate structure and the hole transport layer, and will affect the uniformity of the perovskite precursor solution spreading on the hole transport layer, thereby affecting the photoelectric conversion efficiency and stability of the perovskite solar cell. SUMMARY

[0003] The present application provides a perovskite solar cell, a preparation method thereof and a photovoltaic module, which aims to improve the contact uniformity between the hole transport layer and the substrate structure or the perovskite absorption layer, and improve the electrochemical performance of the perovskite solar cell.

[0004] The present application provides a perovskite solar cell, a preparation method thereof and a photovoltaic module, which aims to improve the contact uniformity between the hole transport layer and the substrate structure or the perovskite absorption layer, and improve the electrochemical performance of the perovskite solar cell. ， ,3 , :4,5] thieno [3,2-b] indol-9-yl) butyl) phosphonic acid, (4-(5H-benzo [4,5] thieno [3,2-c] indol-9-yl) butyl) phosphonic acid, ((9H-carbazole-3,6-diyl) bis (4,1-phenylene)) bisphosphonic acid.

[0005] In some embodiments, in the hole transport layer, the mass ratio of the first material and the second material is 1: (1-5).

[0006] In some embodiments, the first material includes at least one of poly-2-[(2-chlorophenyl) (phenyl) amino] ethyl benzoate, poly-4-phenylacridine derivative, 4-(3,6-dimethyl-9H-carbazole-9-yl) butyl) phosphonic acid, (4-(3,6-dimethyl-9H-carbazole-9-yl) butyl) phosphonic acid.

[0007] In some embodiments, the thickness of the hole transport layer is 0.5-1 nm.

[0008] In some embodiments, the perovskite absorption layer has a thickness of 500-700 nm.

[0009] In some embodiments, the electron transport layer has a thickness of 15-20 nm.

[0010] In some embodiments, the substrate structure is a transparent conductive substrate or a silicon substrate, which includes at least one crystalline silicon cell and / or amorphous silicon cell.

[0011] In some embodiments, the substrate structure is a silicon substrate, and a connecting layer is arranged between the silicon substrate and the hole transport layer.

[0012] In some embodiments, the hole transport layer includes an organic layer and an inorganic layer, the organic layer includes the first material and the second material, and the inorganic layer is arranged between the connecting layer and the organic layer.

[0013] Embodiments of the present application also propose a preparation method of a perovskite solar cell, including the following steps: A hole transport layer precursor solution is prepared, which includes a first material and a second material, the first material is a carbazole-based phosphonic acid compound, and the second material includes at least one of (4-(pyren-1-yl)phenyl)phosphonic acid, (4-(6-fluoro-9H-thieno[2 ， ,3 , :4,5] thieno[3,2-b]indol-9-yl)butyl)phosphonic acid, (4-(5H-benzo[4,5]thieno[3,2-c]indol-9-yl)butyl)phosphonic acid, ((9H-carbazole-3,6-diyl)bis(4,1-phenylene))bisphosphonic acid; The hole transport layer precursor solution is coated on one side of a substrate structure to form a hole transport layer on the substrate structure. A perovskite absorption layer and an electron transport layer are sequentially arranged on the side of the hole transport layer away from the substrate structure.

[0014] In some embodiments, the mass ratio of the first material to the second material in the hole transport material layer precursor solution is 1:(1-5).

[0015] Embodiments of the present application also propose a photovoltaic module, which includes the perovskite solar cell as described above.

[0016] Compared with the prior art, the technical solution has at least the following technical effects: The technical scheme of the present application improves the contact uniformity between the hole transport layer and the substrate structure and between the perovskite absorption layer in the perovskite solar cell, optimizes the energy level matching between the hole transport layer and the perovskite absorption layer, reduces the non-radiative recombination of the perovskite solar cell, and improves the carrier extraction rate of the perovskite solar cell, so that the overall electrochemical performance of the perovskite solar cell is effectively improved. In the perovskite solar cell of the present application, the hole transport layer comprises a first material and a second material, and the phosphoric acid groups in the two materials have an anchoring synergistic effect on the silicon-based substrate structure; compared with the traditional carbazole-based hole transport material, the addition of the second material enhances the anchoring effect of the hole transport layer material on the silicon-based substrate structure, so that the hole transport layer material can be deposited more uniformly on the silicon-based substrate structure, overcoming the thickness sensitivity and insufficient coverage problem of the traditional carbazole-based hole transport layer material; and the hole transport layer material can also improve the wettability of the perovskite precursor solution by adjusting the surface energy, so that the perovskite precursor solution can be uniformly spread on the surface of the hole transport layer during the preparation of the perovskite absorption layer. In addition, the hole transport layer of the present application also has a good buried substrate passivation effect, can passivate interface defects, inhibit non-radiative recombination, and enhance the hole mobility of the hole transport layer, thereby further improving the overall electrochemical performance of the perovskite solar cell. BRIEF DESCRIPTION OF DRAWINGS

[0017] The present application will be further described below in conjunction with the drawings and examples.

[0018] Figure 1 The structure of the perovskite solar cell in an embodiment of the present application is shown in the figure.

[0019] Reference signs: DETAILED DESCRIPTION

[0020] In order to better understand the technical scheme of the present application, the embodiments of the present application will be described in detail below in conjunction with the drawings.

[0021] It should be clear that the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0022] The terms used in the embodiments of the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0023] It should be understood that the term "and / or" used in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this article generally indicates that the preceding and following related objects have an "or" relationship.

[0024] In this embodiment, the photovoltaic module includes a laminate and a frame, with the frame mounted on the edge of the laminate. Specifically, the laminate includes photovoltaic glass, a first encapsulating film, a cell layer, a second encapsulating film, and a backsheet stacked sequentially; or, the laminate includes first photovoltaic glass, a first encapsulating film, a cell layer, a second encapsulating film, and second photovoltaic glass stacked sequentially. The cell layer includes multiple parallel cell strings, each cell string including multiple cells connected in series, and each cell being a whole cell or a cut piece of a whole cell.

[0025] In this embodiment of the application, at least a portion of the solar cells are perovskite solar cells 100.

[0026] Please see Figure 1 In this embodiment, the perovskite solar cell 100 includes a substrate structure 110 and a hole transport layer 140, a perovskite absorber layer 150, and an electron transport layer 160, which are sequentially stacked on one side of the substrate structure 110 from near to far. The hole transport layer 140 includes a first material and a second material. The first material is a phosphonic acid compound containing a carbazole group, and the second material includes (4-(pyrene-1-yl)phenyl)phosphonic acid (PhPAPy), (4-(6-fluoro-9H-thiophene[2])phosphonic acid, and (4-(6-fluoro-9H-thiophene[2])phosphonic acid. ， 3 , At least one of [4,5]thieno[3,2-b]indol-9-yl)butyl)phosphonic acid (KF), (4-(5H-benzo[4,5]thieno[3,2-c]indol-9-yl)butyl)phosphonic acid (THPC), and ((9H-carbazole-3,6-diyl)bis(4,1-phenylene))bisphosphonic acid (2PhPA-CzH).

[0027] In this embodiment, the perovskite solar cell 100 can be either a small-area perovskite solar cell 100 or a large-area perovskite solar cell 100. The specific ranges of small-area and large-area here are determined according to common understanding in the art.

[0028] In this embodiment of the application, the perovskite solar cell 100 can be a single cell or a stacked cell, wherein the stacked cell can be a 2T cell, a 4T cell, etc.

[0029] In the embodiments of the present application, the substrate structure 110 can be a transparent conductive substrate, a silicon substrate, or other commonly used conductive substrates in the art. Among them, the silicon substrate can be composed of at least one crystalline silicon cell, at least one amorphous silicon cell, or composed of at least one crystalline silicon cell and at least one amorphous silicon cell.

[0030] In the embodiments of the present application, the hole transport layer 140, the perovskite absorption layer 150, and the electron transport layer 160 form a perovskite single cell. In some embodiments, the perovskite solar cell 100 includes a bottom cell and a top cell stacked from bottom to top; wherein the bottom cell is composed of the substrate structure 110, and the bottom cell includes at least one silicon cell selected from any one of a crystalline silicon cell and an amorphous silicon cell, and if the bottom cell includes a plurality of silicon cells, the plurality of silicon cells are stacked; the top cell includes one or more perovskite single cells, and if the top cell includes a plurality of perovskite single cells, the plurality of perovskite single cells are stacked from top to bottom.

[0031] In the embodiments of the present application, the crystalline silicon cell can be selected from any one of a TOPCon (tunnel oxide passivated contact cell), an HJT (heterojunction cell), an IBC (interdigitated back contact cell), a PERC (passivated emitter and rear contact cell), or other commonly used crystalline silicon cells in the art, which are not particularly limited in the embodiments of the present application, and can be adjusted by those skilled in the art according to actual application scenarios.

[0032] It should be noted that when the top cell includes a plurality of crystalline silicon cells, the types of the plurality of crystalline silicon cells can be the same or different.

[0033] In the embodiments of the present application, the amorphous silicon cell can be selected from any one of a single-junction amorphous silicon cell, an amorphous silicon stacked cell (such as a double-junction / three-junction stacked cell), or other commonly used amorphous silicon cells in the art, which are not particularly limited in the embodiments of the present application, and can be adjusted by those skilled in the art according to actual application scenarios.

[0034] The technical scheme of the present application improves the contact uniformity between the hole transport layer 140 and the substrate structure 110 and the perovskite absorption layer 150 in the perovskite solar cell 100, optimizes the energy level matching between the hole transport layer 140 and the perovskite absorption layer 150, reduces the non-radiative recombination of the perovskite solar cell 100, and improves the carrier extraction rate of the perovskite solar cell 100, so that the overall electrochemical performance of the perovskite solar cell 100 is effectively improved. In the perovskite solar cell 100 of the present application, the hole transport layer 140 includes a first material and a second material, and the phosphonic acid groups in the two materials have an anchoring synergistic effect on the silicon-based substrate structure 110. Compared with traditional carbazole-based hole transport materials, the addition of the second material enhances the anchoring effect of the hole transport layer 140 material on the silicon-based substrate structure 110, so that the hole transport layer 140 material can be deposited more uniformly on the silicon-based substrate structure 110, overcoming the thickness sensitivity and insufficient coverage problems of traditional carbazole-based hole transport layer 140 materials. Moreover, the hole transport layer 140 material can also improve the wettability of the perovskite precursor solution by adjusting the surface energy, so that the perovskite precursor solution can spread uniformly on the surface of the hole transport layer 140 during the preparation of the perovskite absorption layer 150. In addition, the hole transport layer 140 of the present application also has good buried substrate passivation effect, can passivate interface defects, inhibit non-radiative recombination, and enhance the hole mobility of the hole transport layer 140, thereby further improving the overall electrochemical performance of the perovskite solar cell 100.

[0035] In some embodiments, in the hole transport layer 140, the mass ratio of the first material to the second material is 1: (1~5). Within this mass ratio range, the first material and the second material synergistically anchor the substrate structure 110, and the film-forming property, thickness sensitivity, etc. of the hole transport layer 140 material are controlled within an appropriate range, the energy level matching between the hole transport layer 140 and the perovskite absorption layer 150 is high, which is beneficial to improving the overall electrochemical performance of the perovskite solar cell 100.

[0036] In some embodiments, the first material includes at least one of Poly-2PACz (poly-2-[(2-chlorophenyl)(phenyl)amino]benzoic acid ethyl ester), Poly-4PACz (poly-4-phenylacridine derivative), tBu-4PACz (4-(3,6-dimethyl-9H-carbazol-9-yl)butyl) phosphonic acid), and GM-4PACz ((4-(3,6-dimethyl-9H-carbazol-9-yl)butyl) phosphonic acid).

[0037] In some embodiments, the thickness of the hole transport layer 140 is 0.5 nm to 1 nm, and can be 0.5 nm, 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm or any value therebetween, which can be adjusted by those skilled in the art according to actual application requirements.

[0038] In some embodiments, the thickness of the perovskite absorption layer 150 is 500 nm to 700 nm, and can be 500 nm, 550 nm, 600 nm, 650 nm, 700 nm or any value therebetween, which can be adjusted by those skilled in the art according to actual application requirements.

[0039] In some embodiments, the thickness of the electron transport layer 160 is 15 nm to 20 nm, and can be 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm or any value therebetween, which can be adjusted by those skilled in the art according to actual application requirements.

[0040] Please refer to Figure 1 In some embodiments, the substrate structure 110 is a silicon substrate, and a connecting layer 130 is arranged between the silicon substrate and the hole transport layer 140. The hole transport layer 140, the perovskite absorption layer 150 and the electron transport layer 160 form a top cell, and the silicon substrate serves as a bottom cell. The connecting layer 130 is used to realize efficient and low-loss electrical connection and optical transmission between the top cell and the bottom cell, so that the top cell and the bottom cell can work cooperatively like a cell.

[0041] In some embodiments, the material of the connecting layer 130 can be ITO (indium tin oxide), IZO (indium zinc oxide) or the like.

[0042] In some embodiments, the thickness of the connecting layer 130 is 15 nm to 20 nm, and can be 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm or any value therebetween, which can be adjusted by those skilled in the art according to actual application requirements.

[0043] Please continue to refer to Figure 1 In some embodiments, the hole transport layer 140 includes an organic layer 142 and an inorganic layer 141, the organic layer 142 includes a first material and a second material, and the inorganic layer 141 is arranged between the connecting layer 130 and the organic layer 142.

[0044] The hole transport layer in the traditional solar cell is directly composed of inorganic materials, and the perovskite absorption layer is usually directly deposited on the inorganic materials. Such perovskite solar cells have the following problems: the perovskite precursor solution has poor spreading on the hole transport layer, the coverage of the formed perovskite absorption layer on the hole transport layer is insufficient, the film thickness is uneven, and the uniformity of the contact between the electron transport layer and the silicon substrate is affected. In order to solve this technical problem, the person skilled in the art attempts to use an organic layer and an inorganic layer to form a hole transport layer (for example: a hole transport layer composed of an inorganic layer and an organic layer prepared from a carbazole-based hole material containing a phosphonic acid group and (2-(pyrene-1-yl)ethyl) phosphonic acid). Although such a structure can solve the problem of insufficient coverage of the perovskite absorption layer on the hole transport layer, it also produces a new technical problem: the buried bottom passivation effect of such a hole transport layer is poor, and the perovskite buried interface needs to be passivated before laying the perovskite absorption layer.

[0045] The present application improves the organic layer 142 in the hole transport layer 140. The organic layer 142 is mixed with at least one material selected from the group consisting of a carbazole-based phosphonic acid compound and (4-(pyrene-1-yl)phenyl) phosphonic acid, (4-(6-fluoro-9H-thieno[2 ， ,3 , :4,5] thieno[3,2-b]indol-9-yl)butyl) phosphonic acid, ((9H-carbazole-3,6-diyl)bis(4,1-phenylene)) bisphosphonic acid. These materials have a synergistic effect, not only solving the problem of insufficient coverage of the perovskite absorption layer 150 on the hole transport layer 140, but also having good buried bottom passivation effect, passivating interface defects, inhibiting non-radiative recombination, and simplifying the preparation method of the perovskite solar cell 100, so that the perovskite buried interface does not need to be passivated before laying the perovskite absorption layer 150.

[0046] In the above embodiments, the material of the inorganic layer 141 has multiple choices. In some embodiments, the material of the inorganic layer 141 includes one or more of nickel oxide, cuprous thiocyanate, cuprous oxide, and cobalt oxide; these materials have good hole transport performance and stability, and can efficiently transport holes to collect and transport the holes generated by the perovskite absorption layer 150 to the substrate structure 110.

[0047] In some embodiments, the thickness of the inorganic layer 141 is 2-8 nm, and can be 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm or any value therebetween. A suitable thickness of the inorganic layer 141 can ensure effective transmission of holes while avoiding increased resistance and light absorption loss caused by an excessively thick inorganic layer 141. Of course, the thickness of the inorganic layer 141 can be adjusted according to actual application requirements by those skilled in the art.

[0048] In the embodiments of the present application, the material of the electron transport layer 160 can be selected from one or more of the following: (titanium dioxide), (tin dioxide), (zinc oxide), (indium zinc oxide), PCBM ([6,6]-Phenyl-C61-butyric acid methylester), , BCP (Bathocuproine), , tin sulfide ( ), carbon nitride ( ), and the like.

[0049] In some embodiments, the electron transport layer 160 is composed of a layer of and a layer of ZnO, and a layer of are sequentially stacked from the inside out on the side of the perovskite absorption layer 150 away from the hole transport layer 140.

[0050] In some embodiments, the side of the electron transport layer 160 away from the perovskite absorption layer 150 is further provided with a TCO layer (transparent conductive oxide layer). The material of the TCO layer can be selected from one or more of IZO, ZnO, CdO, and the like.

[0051] In some embodiments, the side of the electron transport layer 160 away from the perovskite absorption layer 150 is provided with an electrode 170, which is referred to as a first electrode. The material of the first electrode can be selected from conventional materials in the art, such as Au, Ag, Al, Cu, and the like, which are not particularly limited in the embodiments of the present application and can be selected according to actual requirements by those skilled in the art.

[0052] In some embodiments, the side of the substrate structure 110 away from the hole transport layer 140 is also provided with an electrode 170, which is referred to as a second electrode. The material of the second electrode can be selected from conventional materials in the art, such as Au, Ag, Al, Cu, and the like, which are not particularly limited in the embodiments of the present application and can be selected according to actual requirements by those skilled in the art.

[0053] Secondly, this application also proposes a method for preparing the perovskite solar cell 100 described above.

[0054] In this embodiment of the application, the preparation method includes the following steps: S10. Prepare a hole transport layer 140 precursor solution. The hole transport layer 140 precursor solution includes a first material and a second material. The first material is a phosphonic acid compound containing a carbazole group. The second material includes (4-(pyrene-1-yl)phenyl)phosphonic acid, (4-(6-fluoro-9H-thiophene[2])phosphonic acid, and (6-fluoro-9H-thiophene[2])phosphonic acid. ， 3 , At least one of the following: (4,5)thieno[3,2-b]indol-9-yl)butyl)phosphonic acid, (4-(5H-benzo[4,5]thieno[3,2-c]indol-9-yl)butyl)phosphonic acid, and ((9H-carbazole-3,6-diyl)bis(4,1-phenylene))bisphosphonic acid; S20. The hole transport layer 140 precursor solution is coated on one side of the substrate structure 110, and the hole transport layer 140 is formed on the substrate structure 110. S30. A perovskite absorption layer 150 and an electron transport layer 160 are disposed on the side of the hole transport layer 140 facing away from the substrate structure 110.

[0055] In some embodiments, the specific steps of S10 include: Using ethanol / DMSO (3:1) as a solvent, the first material was prepared into a first solution of 1 mg / L; Using ethanol as a solvent, the second material was prepared into a second solution of 1 mg / L; The first solution and the second solution were mixed evenly at a volume ratio of 1:(1~5) to obtain the hole transport layer 140 precursor solution.

[0056] In some embodiments, in step S20, a precursor solution for the hole transport layer 140 is coated onto one side surface of the substrate structure 110 using a spin coating method.

[0057] In some embodiments, prior to step S30, the method for preparing the perovskite solar cell 100 further includes the step of: preparing a perovskite precursor solution.

[0058] In some embodiments, the perovskite precursor solution includes at least one of CsI, PbI2, PbBr2, FAI (formamidinium hydroiodide), and MAI (methylamine iodide).

[0059] In some embodiments, in step S30, a perovskite absorption layer 150 is formed on the surface of the hole transport layer 140 by spin coating.

[0060] In some embodiments, after step S30, there is further a step S40 of disposing a TCO layer on the electron transport layer 160.

[0061] In some embodiments, in step S40, the TCO layer is deposited on the electron transport layer 160 by a magnetron sputtering process.

[0062] In some embodiments, after step S40, there is further a step S50 of disposing an electrode 170 on the TCO layer.

[0063] In some embodiments, the substrate structure 110 is a silicon substrate, and a connecting layer 130 is disposed between the silicon substrate and the hole transport layer 140. Before step S20, the method of preparing the perovskite solar cell 100 further comprises a step of disposing the connecting layer 130 on the silicon substrate.

[0064] In some embodiments, the hole transport layer 140 in the perovskite solar cell 100 comprises an organic layer 142 and an inorganic layer 142, the organic layer 142 comprises a first material and a second material, and the inorganic layer 141 is disposed between the connecting layer 130 and the organic layer 142. In this embodiment, the organic layer 142 is prepared as described in step S20, and before step S20, the method of preparing the perovskite solar cell 100 further comprises a step of disposing the inorganic layer 141 on the connecting layer 130. In this embodiment, the hole transport layer 140 precursor solution in step S20 is directly coated on the inorganic layer 141.

[0065] The perovskite solar cell 100 of the present application is further described below by more specific embodiments.

[0066] Embodiment 1 (perovskite solar cell device with an area of 1 cm 1cm): (1) Preparation of hole transport layer precursor solution: 1 mg of POLY-2PACZ (poly-2-[(2-chlorophenyl)(phenyl)amino]benzoic acid ethyl ester) was weighed and dissolved in 1 mL of ethanol / DMSO (3:1) solution to prepare a first solution; then 1 mg of (4-(pyrene-1-yl)phenyl)phosphonic acid was weighed and dissolved in 1 mL of ethanol solution to prepare a second solution; then the first solution and the second solution were mixed uniformly at a volume ratio of 1:2 to obtain the hole transport layer precursor solution.

[0067] (2) Preparation of hole transport layer: In a glove box, an appropriate amount of hole transport layer precursor solution was uniformly dropped onto a silicon substrate with a size of 1 cm 1cm, and spin-coated at 4000-5000 rpm for 20-30 seconds, and then annealed at 100-140°C for 10 minutes, and then cooled to room temperature to obtain a Si / hole transport layer composite layer.

[0068] (3) Preparation of perovskite absorption layer: prepare perovskite precursor solution by uniformly mixing CsI, PbI2, PbBr2, FAI and MAI in DMF and DMSO according to a certain molar ratio; take 50 μl of the perovskite precursor solution to spread on the surface of the hole transport layer of the Si / hole transport layer composite layer, spin-coat at 3000-5000 rpm for 20-30 seconds, then anneal at 90-100°C for 10 minutes, and then cool to room temperature to obtain a Si / hole transport layer / perovskite absorption layer composite layer.

[0069] (4) Preparation of electron transport layer: use an evaporation machine to deposit 15 nm of C 60 thin film on the surface of the perovskite absorption layer of the Si / hole transport layer / perovskite absorption layer composite layer. 60 Subsequently, use an ALD device to deposit SnO2 on the C 60 thin film to obtain a Si / hole transport layer / perovskite absorption layer / C 60 / SnO2 composite layer.

[0070] (5) Preparation of TCO layer: use magnetron sputtering to deposit an IZO film layer to obtain a Si / hole transport layer / perovskite absorption layer / C 60 / SnO2 / IZO composite layer.

[0071] (6) Preparation of electrode: place the composite layer obtained in step (5) in a vacuum evaporation box, evaporate Ag (1000 nm) on the SnO2 layer to obtain a perovskite solar cell.

[0072] Example 2 The difference from Example 1 is that in step (1): The first solution and the second solution are mixed uniformly according to a volume ratio of 1:1.

[0073] Example 3 The difference from Example 1 is that in step (1): The first solution and the second solution are mixed uniformly according to a volume ratio of 1:5.

[0074] Example 4 The difference from Example 1 is that in step (1): Replace (4-(pyren-1-yl)phenyl)phosphonic acid in step (1) with (4-(6-fluoro-9H-thieno[2 ， ,3 , :4,5]thieno[3,2-b]indol-9-yl)butyl)phosphonic acid.

[0075] Example 5 The difference from Example 1 is that in step (1): (4-(pyren-1-yl)phenyl)phosphonic acid in step (1) is replaced by ((9H-carbazole-3,6-diyl)bis(4,1-phenylene))bisphosphonic acid.

[0076] Example 6 The difference from Example 1 is that step (1) is: (4-(pyren-1-yl)phenyl)phosphonic acid in step (1) is replaced by ((9H-carbazole-3,6-diyl)bis(4,1-phenylene))bisphosphonic acid.

[0077] Example 7 (1) 1 cm A IZO thin film is deposited on one side of a 1 cm silicon substrate to obtain a Si / IZO composite structure.

[0078] (2) Preparation of a hole transport layer precursor solution: 1 mg of POLY-2PACZ (2-[(2-chlorophenyl)(phenyl)amino]benzoic acid ethyl ester) is weighed and dissolved in 1 mL of an ethanol / DMSO (3:1) solution to obtain a first solution; then 1 mg of (4-(pyren-1-yl)phenyl)phosphonic acid is weighed and dissolved in 1 mL of an ethanol solution to obtain a second solution; then the first solution and the second solution are mixed uniformly at a volume ratio of 1:2 to obtain a hole transport layer precursor solution.

[0079] (3) Preparation of a hole transport layer: a NiOx thin film layer is deposited on one side surface of the IZO thin film layer of the Si / IZO composite structure to obtain a Si / IZO / NiOx composite layer; then, in a glove box, an appropriate amount of the hole transport layer precursor solution is added dropwise to the surface of the NiOx of the Si / IZO / NiOx composite layer, and spin-coated at 4000-5000 rpm for 20-30 seconds, and then annealed at 100-140°C for 10 minutes, and then cooled to room temperature to obtain a Si / IZO / hole transport layer composite layer. x x (3) Preparation of a hole transport layer: a NiOx thin film layer is deposited on one side surface of the IZO thin film layer of the Si / IZO composite structure to obtain a Si / IZO / NiOx composite layer; then, in a glove box, an appropriate amount of the hole transport layer precursor solution is added dropwise to the surface of the NiOx of the Si / IZO / NiOx composite layer, and spin-coated at 4000-5000 rpm for 20-30 seconds, and then annealed at 100-140°C for 10 minutes, and then cooled to room temperature to obtain a Si / IZO / hole transport layer composite layer.

[0080] (3) Preparation of a hole transport layer: a NiOx thin film layer is deposited on one side surface of the IZO thin film layer of the Si / IZO composite structure to obtain a Si / IZO / NiOx composite layer; then, in a glove box, an appropriate amount of the hole transport layer precursor solution is added dropwise to the surface of the NiOx of the Si / IZO / NiOx composite layer, and spin-coated at 4000-5000 rpm for 20-30 seconds, and then annealed at 100-140°C for 10 minutes, and then cooled to room temperature to obtain a Si / IZO / hole transport layer composite layer.

[0081] ​(4) Preparation of the electron transport layer: 15 nm C 60 thin film: Subsequently, Sn02was deposited on the C 60 thin film using an ALD device to obtain a Si / IZO / hole transport layer / perovskite absorber / C 60 / Sn02composite layer.

[0082] (5) Preparation of the TCO layer: IZO film layer was deposited using magnetron sputtering to obtain a Si / IZO / hole transport layer / perovskite absorber / C 60 / Sn02 / IZO composite layer.

[0083] (6) Preparation of the electrode: The composite layer obtained in step (5) was placed in a vacuum evaporation box, and Ag (1000 nm) was evaporated on the Sn02layer to obtain a perovskite solar cell.

[0084] Example 8 The difference between Example 7 and Example 8 is step (1): POLY-2PACZ in step (1) was replaced by GM-4PACz.

[0085] Example 9 The difference between Example 7 and Example 9 is step (1): POLY-2PACZ in step (1) was replaced by tBu-4PACz.

[0086] Example 10 The difference between Example 7 and Example 10 is step (1): POLY-2PACZ in step (1) was replaced by Poly-4PACz.

[0087] Comparative Example 1 The difference between Example 1 and Comparative Example 1 is step (1): (1) Preparation of the hole transport layer precursor solution: 1 mg of (4-(pyrene-1-yl)phenyl)phosphonic acid was weighed and dissolved in 1 mL of an ethanol solution to obtain a hole transport layer precursor solution.

[0088] Comparative Example 2 The difference between Example 1 and Comparative Example 2 is step (1): (1) Preparation of the hole transport layer precursor solution: 1 mg of POLY-2PACZ (2-[(2-chlorophenyl)(phenyl)amino]benzoic acid ethyl ester) was weighed and dissolved in 1 mL of an ethanol / DMSO (3:1) solution to obtain a hole transport layer precursor solution.

[0089] Comparative Example 3 The difference from Example 7 is that step (1) is changed as follows: (1) Preparation of the hole transport layer precursor solution: 1 mg of POLY-2PACZ (2-[(2-chlorophenyl)(phenyl)amino]benzoic acid ethyl ester) was weighed and dissolved in 1 mL of an ethanol / DMSO (3:1) solution to obtain the hole transport layer precursor solution.

[0090] Comparative Example 4 The difference from Example 7 is that step (1) is changed as follows: (1) Preparation of the hole transport layer precursor solution: 1 mg of (4-(pyren-1-yl)phenyl)phosphonic acid was weighed and dissolved in 1 mL of an ethanol solution to obtain the hole transport layer precursor solution.

[0091] Comparative Example 5 The difference from Example 7 is that: (4-(pyren-1-yl)phenyl)phosphonic acid in step (1) is replaced by (2-(pyren-1-yl)ethyl)phosphonic acid.

[0092] Comparative Example 6 The difference from Example 7 is that: (4-(pyren-1-yl)phenyl)phosphonic acid in step (1) is replaced by (2-(pyren-1-yl)ethyl)phosphonic acid, and POLY-2PACZ is replaced by [2-(9H-carbazol-9-yl)phenyl]phosphonic acid.

[0093] Comparative Example 7 (1) A 1 cm An IZO thin film was deposited on one side of a 1 cm silicon substrate to obtain a Si / IZO composite structure.

[0094] (2) Preparation of the hole transport layer precursor solution: 1 mg of POLY-2PACZ (2-[(2-chlorophenyl)(phenyl)amino]benzoic acid ethyl ester) was weighed and dissolved in 1 mL of an ethanol / DMSO (3:1) solution to obtain a first solution; then 1 mg of (2-(pyren-1-yl)ethyl)phosphonic acid was weighed and dissolved in 1 mL of an ethanol solution to obtain a second solution; then the first solution and the second solution were mixed in a volume ratio of 1:2 to obtain the hole transport layer precursor solution.

[0095] (3) Preparation of the hole transport layer: a NiOx thin film layer was deposited on one side surface of the IZO thin film layer of the Si / IZO composite structure to obtain a Si / IZO / NiOx composite layer; then, in the glove box, an appropriate amount of the hole transport layer precursor solution was added dropwise to the NiO x x thin film layer of the Si / IZO / NiO xThe surface of the IZO / hole transport layer composite layer is spin-coated with 4000-5000 rpm for 20-30 seconds, and then annealed at 100-140°C for 10 minutes, and then cooled to room temperature to obtain a Si / IZO / hole transport layer composite layer.

[0096] (3) Perovskite buried bottom interface passivation: an alumina ethanol solution is selected, which is diluted at a volume ratio of 1: (100-300) to obtain a lower interface passivation solution, and an appropriate amount of the lower interface passivation solution is uniformly added to the surface of the hole transport layer of the Si / IZO / hole transport layer composite layer, spin-coated at 4000-5000 rpm for 20-30 seconds, and then annealed at 100-140°C for 10 minutes, and then cooled to room temperature to obtain a Si / IZO / hole transport layer composite layer / lower interface passivation layer composite layer.

[0097] (4) Preparation of perovskite absorption layer: CsI, PbI2, PbBr2, FAI and MAI are uniformly mixed in DMF and DMSO according to a certain molar ratio to prepare a perovskite precursor solution; 50 μl of the perovskite precursor solution is spread on the surface of the lower interface passivation layer of the Si / IZO / hole transport layer / lower interface passivation layer composite layer, spin-coated at 3000-5000 rpm for 20-30 seconds, and then annealed at 90-100°C for 10 minutes, and then cooled to room temperature to obtain a Si / IZO / hole transport layer / lower interface passivation layer / perovskite absorption layer composite layer.

[0098] (5) Preparation of electron transport layer: a C 60 thin film is deposited on the surface of the perovskite absorption layer of the Si / hole transport layer / perovskite absorption layer composite layer using an evaporation machine. 60 Then SnO2 is deposited on the C 60 thin film using an ALD device to obtain a Si / IZO / hole transport layer / lower interface passivation layer / perovskite absorption layer / C 60 / SnO2 composite layer.

[0099] (6) Preparation of TCO layer: IZO film layer is deposited using a magnetron sputtering to obtain a Si / IZO / hole transport layer / lower interface passivation layer / perovskite absorption layer / C 60 / SnO2 / IZO composite layer.

[0100] (7) Preparation of electrode: the composite layer obtained in step (5) is placed in a vacuum evaporation box, and Ag (1000 nm) is evaporated on the SnO2 layer to obtain a perovskite solar cell.

[0101] Performance test: The power of the devices prepared in the above examples and comparative examples is adjusted to 100 mw / cm 2To simulate AM 1.5G radiation standard, the current and voltage values of the device were read by connecting a computer reader to a Keithley 2450 power meter. Before the J-V curve measurement, the light intensity was calibrated using a Newport standard silicon cell 91150, the device was taken in the forward and reverse scan mode, and the scan rate was 0.05 V / s. The test results are shown in Table 1 below:

[0102] Analysis: Comparing Example 1 with Comparative Examples 1 and 2, or by comparing Example 7 with Comparative Examples 3 and 4, it can be proved that the first material and the second material in the hole transport layer have a synergistic effect, and compared with using one of the first material and the second material as the hole transport layer material or the organic layer material of the hole transport layer of the perovskite solar cell alone, using the material mixed from the first material and the second material as the hole transport layer material or the organic layer material of the hole transport layer of the perovskite solar cell has a stronger anchoring effect on the substrate structure, and can be more uniformly deposited on the silicon-based substrate type substrate structure, which is more conducive to improving the overall electrochemical performance of the perovskite solar cell.

[0103] Comparing Example 7 with Comparative Examples 5-7 can prove that using the material mixed from the first material and the second material as the hole transport layer material or the organic layer material of the hole transport layer of the perovskite solar cell in the present application is conducive to improving the interface contact of the perovskite and improving the coverage uniformity of the perovskite absorption layer, which solves the problem of passivation treatment of the perovskite buried interface before laying the perovskite absorption layer in the prior art, and simplifies the preparation process.

[0104] The above is only a preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A perovskite solar cell, characterized in that, The system includes a substrate structure and, from near to far, a hole transport layer, a perovskite absorber layer, and an electron transport layer sequentially stacked on one side of the substrate structure. The hole transport layer comprises a first material and a second material. The first material is a phosphonic acid compound containing a carbazole group, and the second material comprises (4-(pyrene-1-yl)phenyl)phosphonic acid, (4-(6-fluoro-9H-thiophene[2])... ， 3 , At least one of the following: (4,5)thieno[3,2-b]indol-9-yl)butyl)phosphonic acid, (4-(5H-benzo[4,5]thieno[3,2-c]indol-9-yl)butyl)phosphonic acid, and ((9H-carbazole-3,6-diyl)bis(4,1-phenylene))bisphosphonic acid.

2. The perovskite solar cell as described in claim 1, characterized in that, In the hole transport layer, the mass ratio of the first material to the second material is 1:(1~5).

3. The perovskite solar cell according to claim 1, characterized in that, The first material includes at least one of poly-2-[(2-chlorophenyl)(phenyl)amino]benzoate, poly-4-phenylacridine derivative, 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid, and (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid.

4. The perovskite solar cell according to claim 1, characterized in that, The thickness of the hole transport layer is 0.5 nm to 1 nm; The thickness of the perovskite absorber layer is 500 nm to 700 nm; The thickness of the electron transport layer is 15nm~20nm.

5. The perovskite solar cell according to claim 1, characterized in that, The substrate structure is a transparent conductive substrate or a silicon substrate, and the silicon substrate includes at least one crystalline silicon cell and / or an amorphous silicon cell.

6. The perovskite solar cell according to any one of claims 1-5, characterized in that, The substrate structure is a silicon substrate, and a connecting layer is disposed between the silicon substrate and the hole transport layer.

7. The perovskite solar cell according to claim 6, characterized in that, The hole transport layer includes an organic layer and an inorganic layer. The organic layer includes the first material and the second material, and the inorganic layer is disposed between the connecting layer and the organic layer.

8. A method for fabricating a perovskite solar cell, characterized in that, Includes the following steps: A hole transport layer precursor solution is prepared, comprising a first material and a second material. The first material is a phosphonic acid compound containing a carbazole group, and the second material comprises (4-(pyrene-1-yl)phenyl)phosphonic acid, (4-(6-fluoro-9H-thiophene[2])phosphonic acid, and (4-(6-fluoro-9H-thiophene[2])phosphonic acid. ， 3 , At least one of the following: (4,5)thieno[3,2-b]indol-9-yl)butyl)phosphonic acid, (4-(5H-benzo[4,5]thieno[3,2-c]indol-9-yl)butyl)phosphonic acid, and ((9H-carbazole-3,6-diyl)bis(4,1-phenylene))bisphosphonic acid; The hole transport layer precursor solution is coated on one side of the substrate structure to form a hole transport layer on the substrate structure. A perovskite absorption layer and an electron transport layer are sequentially disposed on the side of the hole transport layer facing away from the substrate structure.

9. The method for preparing a perovskite solar cell as described in claim 8, characterized in that, In the hole transport layer precursor solution, the mass ratio of the first material to the second material is 1:(1~5).

10. A photovoltaic module, characterized in that, Includes the perovskite solar cell as described in any one of claims 1-7, or includes the perovskite solar cell prepared by the method described in claim 8 or 9.

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