Perovskite / crystalline silicon laminated solar cell, preparation method thereof and photovoltaic module

Abstract

The invention discloses a perovskite / crystalline silicon laminated solar cell, a preparation method thereof and a photovoltaic module. The perovskite / crystalline silicon laminated solar cell provided by the invention comprises a perovskite top cell, a crystalline silicon bottom cell and a composite layer used for connecting the perovskite top cell and the crystalline silicon bottom cell, the perovskite top cell comprises a composite hole transport layer, the composite hole transport layer comprises a first hole transport layer and a second hole transport layer, and the first hole transport layer is in contact with the composite layer; the first hole transport layer is obtained by sputtering a nickel oxide target material by introducing H2 in an oxygen-free sputtering atmosphere, and the second hole transport layer is obtained by sputtering the nickel oxide target material in a hydrogen-free atmosphere. According to the perovskite / crystalline silicon laminated solar cell provided by the invention, the composite hole transport layer can realize better contact matching with the middle composite layer, better charge extraction and collection are carried out on the perovskite light absorption layer, and meanwhile, the perovskite / crystalline silicon laminated solar cell has better conductivity.

Description

Technical Field

[0001] This application relates to the field of photovoltaic materials technology, and more specifically, to a perovskite / crystalline silicon tandem solar cell, its preparation method, and a photovoltaic module. Background Technology

[0002] While perovskite / crystalline silicon tandem solar cells have undergone rapid development and their advantages have become quite apparent, some of their inherent problems have also become increasingly unavoidable as efficiency has gradually improved. Research has revealed that the hole transport layer plays a crucial role in the photoelectric conversion efficiency of the device. Currently used single NiO... x To balance the interfacial contact with the composite layer and the extraction and collection of its own pores, only one optimal film layer can be obtained through optimization. Using a single NiO layer... x In the film layer, the hole transport layer is difficult to achieve contact matching with the composite layer, resulting in hindered interfacial charge transfer; simultaneously, the NiO in contact with the composite layer... x Surface interface defects cause recombination losses. Simultaneously, a single-layer hole transport layer struggles to achieve rapid extraction and collection of hole carriers. This limits the device's flyback effect (FF) and voltage characteristics. OC And further improvements in efficiency.

[0003] Currently NiO x Most thin film fabrications employ solution methods. While nickel oxide nanoparticles synthesized using four different organic bases can effectively modulate the hole transport layer energy levels, improve hole transport characteristics, reduce energy shift relative to the perovskite valence band maximum, and lower ohmic losses to a negligible level, and using nickel oxide as the hole transport layer with PTAA as the interface functional passivation layer can effectively assist hole transport, hinder electron passage, passivate interface defects between the perovskite light-absorbing layer and nickel oxide, and prevent recombination of interface carriers, thereby improving the photovoltaic performance of the device, this approach only focuses on the energy level matching and charge transport between the hole transport layer and the perovskite interface, neglecting the interface energy level matching between the hole transport layer and the intermediate recombination layer. This results in severe contact losses and carrier transport obstruction, limiting further improvements in device efficiency. Summary of the Invention

[0004] The purpose of this application is to overcome the defects of the prior art by providing a perovskite / crystalline silicon tandem solar cell, its preparation method, and a photovoltaic module.

[0005] The technical problem solved by this application is achieved by the following technical solution.

[0006] In a first aspect, this application provides a perovskite / crystalline silicon tandem solar cell, comprising: a perovskite top cell and a crystalline silicon bottom cell, and a composite layer for connecting the perovskite top cell and the crystalline silicon bottom cell;

[0007] The perovskite top solar cell includes a composite hole transport layer, which includes a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is in contact with the composite layer.

[0008] The first hole transport layer was obtained by sputtering a nickel oxide target with H2 in an oxygen-free sputtering atmosphere, and the second hole transport layer was obtained by sputtering a nickel oxide target in a hydrogen-free atmosphere.

[0009] In some embodiments of this application, the composite hole transport layer is a bilayer NiO composed of a first hole transport layer and a second hole transport layer. x Thin film, bilayer NiO x The thickness of the thin film is 11nm-25nm.

[0010] In some embodiments of this application, the thickness of the first hole transport layer is 1nm-5nm.

[0011] In some embodiments of this application, the thickness of the second hole transport layer is 10nm-20nm.

[0012] This application provides a perovskite / crystalline silicon tandem solar cell. The composite hole transport layer includes a first hole transport layer and a second hole transport layer. The first hole transport layer is obtained by sputtering a nickel oxide target with H2 in an oxygen-free sputtering atmosphere. Using nickel oxide as the target, sputtering deposition in a hydrogen-containing atmosphere can deposit high-valence Ni 3+ Ni 4+ Reduced to low-cost Ni 2+ Meanwhile, H + As a shallow donor impurity, it can provide electrons, reducing the hole carrier concentration and exhibiting a low work function, thus achieving energy level matching with the intermediate composite layer. The second hole transport layer is obtained by sputtering a nickel oxide target in a hydrogen-free atmosphere. Using nickel oxide as the target and sputtering deposition in a hydrogen-free atmosphere can ensure the quality of NiO. x The layer has suitable Ni 3+ The increased content of NiO allows the film to have more Ni atom vacancies, resulting in more hole carriers. This enables the construction of a larger built-in electric field in perovskite top cells, while also allowing NiO to... x The layer possesses high conductivity and hole transport capability, thus ensuring the photoelectric conversion efficiency of the perovskite solar cell. The perovskite / crystalline silicon tandem solar cell described above achieves improved photoelectric efficiency by incorporating a composite hole transport layer on the composite layer.

[0013] In some embodiments of this application, the carrier concentration of the first hole transport layer is 1.0 × 10⁻⁶. 17 / cm 3 -6.0×10 18 / cm 3 The carrier mobility is 0.4 cm⁻¹ 2 / Vs-6.0cm 2 / Vs, resistivity 2.6 ohm.cm-10.5 ohm.cm.

[0014] This application provides a perovskite / crystalline silicon tandem solar cell, wherein the composite hole transport layer in the perovskite / crystalline silicon tandem solar cell is a bilayer NiO composed of a first hole transport layer and a second hole transport layer. x The thin film exhibits a low carrier concentration and high carrier mobility in its first hole transport layer. The low carrier concentration reduces the work function of the first hole transport layer, achieving better energy level matching with the composite layer, lowering the contact potential, and resulting in excellent contact. Simultaneously, its high carrier mobility reduces charge accumulation at the interface between the composite layer and the first hole transport layer, enabling rapid charge transport.

[0015] In some embodiments of this application, the carrier concentration of the second hole transport layer is 9.0 × 10⁻⁶. 18 / cm 3 -5.0×10 20 / cm 3 The carrier mobility is 0.01 cm⁻¹ 2 / Vs-0.3cm 2 / Vs, resistivity is 0.4 ohm.cm-2.5 ohm.cm.

[0016] This application provides a perovskite / crystalline silicon tandem solar cell, wherein the composite hole transport layer in the perovskite / crystalline silicon tandem solar cell is a bilayer NiO composed of a first hole transport layer and a second hole transport layer. x The thin film, and the second hole transport layer with a high carrier concentration, can achieve a larger built-in electric field in the perovskite top cell, serving as a hole extraction and collection layer, enabling faster hole extraction and collection. Simultaneously, its high carrier concentration results in low resistivity, reducing the series resistance of the device.

[0017] The composite hole transport layer provided above can achieve better contact matching with the intermediate composite layer, better charge extraction and collection from the perovskite light-absorbing layer, and higher conductivity.

[0018] Secondly, this application also provides a method for fabricating the above-mentioned perovskite / crystalline silicon tandem solar cell, which includes: providing a crystalline silicon base cell; fabricating a composite layer on the crystalline silicon base cell; and fabricating a composite hole transport layer on the side of the composite layer away from the crystalline silicon base cell. The step of fabricating the composite hole transport layer includes the following steps:

[0019] A first hole transport layer is formed by sputtering using a nickel oxide target in a first atmosphere, wherein the first atmosphere contains argon and hydrogen; then, a second hole transport layer is formed by sputtering using a nickel oxide target in a second atmosphere, wherein the second atmosphere contains argon and optional oxygen.

[0020] In some embodiments of this application, the process conditions for forming the first hole transport layer include: using NiO x As the target material, the sputtering pressure was controlled at 0.3 Pa-1.0 Pa, the sputtering temperature at 23 °C-200 °C, and the sputtering power at 100 W-1100 W for NiO sputtering. x Film formation.

[0021] In some embodiments of this application, during the sputtering process, the flow rate of the first atmosphere is controlled as follows: the flow rate of Ar introduced into the chamber is controlled to be 500 sccm-1200 sccm, the flow rate of O2 is 0 sccm, and the flow rate of H2 is 0.1%-3% of the flow rate of Ar.

[0022] This application provides a method for fabricating a perovskite / crystalline silicon tandem solar cell. The method employs radio frequency magnetron sputtering to fabricate the first hole transport layer, and introduces H2 during the fabrication of the first hole transport layer to propagate high-valence Ni. 3+ Ni4 + Reduced to low-cost Ni 2+ Meanwhile, H + As a shallow donor impurity, it can donate electrons, reducing the hole carrier concentration, and has a low work function, achieving energy level matching with the intermediate recombination layer. NiO is produced by introducing H2 under oxygen-free conditions. x The first hole transport layer, formed by film deposition, exhibits high carrier mobility, enabling rapid interfacial charge transport; simultaneously, H + It can passivate NiO x To address the shortcomings of [the system], reduce the recombination loss of holes during transmission.

[0023] In some embodiments of this application, the process conditions for forming the second hole transport layer include: using NiO x As the target material, the sputtering pressure was controlled at 0.3 Pa-1.0 Pa, the sputtering temperature at 23 °C-200 °C, and the sputtering power at 100 W-1100 W for NiO sputtering. x Film formation.

[0024] In some embodiments of this application, during the sputtering process, the flow rates of the second atmosphere are controlled as follows: the Ar flow rate is controlled at 500 sccm-1200 sccm, the O2 flow rate is controlled at 0 sccm-10 sccm, and the H2 flow rate is controlled at 0 sccm.

[0025] This application provides a method for fabricating a perovskite / crystalline silicon tandem solar cell, which employs a radio frequency magnetron sputtering process to prepare a second hole transport layer, and utilizes NiO under hydrogen-free conditions. x The second hole transport layer, which is formed by film deposition, has a higher hole carrier concentration and a lower carrier mobility, as well as a larger built-in electric field, to enable rapid extraction and collection of hole carriers generated by the perovskite light-absorbing layer. At the same time, the second hole transport layer has better conductivity than the first hole transport layer, reducing the overall series resistance of the device.

[0026] Thirdly, this application also provides a perovskite / crystalline silicon tandem solar cell, comprising: a perovskite top cell and a crystalline silicon bottom cell, and a composite layer for connecting the perovskite top cell and the crystalline silicon bottom cell;

[0027] The perovskite top solar cell includes a hole transport layer, which includes a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is in contact with the composite layer.

[0028] The first hole transport layer and the second hole transport layer were prepared using the above-described preparation method.

[0029] This application also provides a perovskite / crystalline silicon tandem solar cell, comprising: a perovskite top cell, a crystalline silicon bottom cell, and a composite layer connecting the perovskite top cell and the crystalline silicon bottom cell. The perovskite top cell includes a composite hole transport layer. A first hole transport layer in the composite hole transport layer can increase charge transport at the interface with the composite layer, and a second hole transport layer serves as a carrier extraction and collection layer, enabling rapid extraction and collection of hole carriers generated by the perovskite light-absorbing layer, thereby achieving NiO... x Higher conductivity reduces the overall series resistance of the device.

[0030] In some embodiments of this application, the application further includes a hole modification layer and a passivation layer, wherein the hole modification layer is located between the second hole transport layer and the perovskite light-absorbing layer, and the passivation layer is located between the perovskite light-absorbing layer and the electron transport layer.

[0031] In some embodiments of this application, it further includes: a buffer layer, a second transparent conductive oxide layer, and an optical antireflection layer stacked on the front side of the electron transport layer.

[0032] In some embodiments of this application, the crystalline silicon bottom cell includes an N-type silicon wafer, a second intrinsic amorphous silicon layer and an N-type doped nanocrystalline silicon layer sequentially disposed on the front side of the N-type silicon wafer, and a first intrinsic amorphous silicon layer, a P-type doped nanocrystalline silicon layer and a first transparent conductive oxide layer sequentially disposed on the back side of the N-type silicon wafer.

[0033] In some embodiments of this application, the battery further includes: a first grid electrode and a second grid electrode. The second grid electrode is disposed on the surface of the perovskite / crystalline silicon tandem solar cell away from the crystalline silicon bottom cell. The second grid electrode penetrates the optical antireflection layer and contacts the second transparent conductive oxide layer to form the positive electrode of the battery. The first grid electrode is disposed on the surface of the perovskite / crystalline silicon tandem solar cell away from the perovskite top cell. The first grid electrode contacts the first transparent conductive oxide layer to form the negative electrode of the battery.

[0034] Fourthly, this application also provides a perovskite / crystalline silicon tandem solar cell, comprising: a perovskite top cell and a crystalline silicon bottom cell, and a composite layer for connecting the perovskite top cell and the crystalline silicon bottom cell, a first grid electrode and a second grid electrode; the perovskite top cell includes a first hole transport layer, a second hole transport layer, a hole modification layer, a perovskite light-absorbing layer, a passivation layer, an electron transport layer, a buffer layer, a second transparent conductive oxide layer and an optical anti-reflection layer sequentially disposed on the front side of the composite layer, the second grid electrode penetrating the optical anti-reflection layer and contacting the second transparent conductive oxide layer to form the positive electrode of the cell; the crystalline silicon bottom cell includes an N-type doped nanocrystalline silicon layer, a second intrinsic amorphous silicon layer, an N-type silicon wafer, a first intrinsic amorphous silicon layer, a P-type doped nanocrystalline silicon layer and a first transparent conductive oxide layer sequentially disposed on the back side of the composite layer, the first grid electrode contacting the first transparent conductive oxide layer to form the negative electrode of the cell.

[0035] Fifthly, this application also provides a photovoltaic module, including the aforementioned perovskite / crystalline silicon tandem solar cell.

[0036] This application also provides a photovoltaic module, which includes the above-mentioned perovskite / crystalline silicon tandem solar cell and also has excellent photoelectric efficiency.

[0037] This application has the following beneficial effects:

[0038] This application provides a perovskite / crystalline silicon tandem solar cell, its fabrication method, and a photovoltaic module. The perovskite / crystalline silicon tandem solar cell provided in this application includes: a perovskite top cell and a crystalline silicon bottom cell, and a composite layer for connecting the perovskite top cell and the crystalline silicon bottom cell; the perovskite top cell includes a composite hole transport layer, which comprises a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is in contact with the composite layer; the first hole transport layer is obtained by sputtering a nickel oxide target with H2 in an oxygen-free sputtering atmosphere, and the second hole transport layer is obtained by sputtering a nickel oxide target with a hydrogen-free atmosphere. The first hole transport layer in the perovskite / crystalline silicon tandem solar cell provided above can increase charge transport at the interface with the composite layer, and the second hole transport layer, as a carrier extraction and collection layer, can quickly extract and collect hole carriers generated by the perovskite light-absorbing layer, achieving higher conductivity and reducing the overall series resistance of the device. Attached Figure Description

[0039] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0040] Figure 1 A schematic diagram of a perovskite / crystalline silicon tandem solar cell;

[0041] Figure Numbers: Composite Layer-100, Crystalline Silicon Bottom Cell-200, First Transparent Conductive Oxide Layer-210, P-Type Doped Nanocrystalline Silicon Layer-220, First Intrinsic Amorphous Silicon Layer-230, N-Type Silicon Wafer-240, Second Intrinsic Amorphous Silicon Layer-250, N-Type Doped Nanocrystalline Silicon Layer-260, Perovskite Top Cell-300, Composite Hole Transport Layer-310, First Hole Transport Layer-310a, Second Hole Transport Layer-310b, Hole Modification Layer-320, Perovskite Light Absorbing Layer-330, Passivation Layer-340, Electron Transport Layer-350, Buffer Layer-360, Second Transparent Conductive Oxide Layer-370, Optical Anti-reflection Layer-380, First Gate Electrode-410, Second Gate Electrode-420. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0043] The following is a detailed description of a perovskite / crystalline silicon tandem solar cell, its fabrication method, and a photovoltaic module provided in the embodiments of this application.

[0044] In a first aspect, embodiments of this application provide a perovskite / crystalline silicon tandem solar cell, comprising: a perovskite top cell 300 and a crystalline silicon bottom cell 200, and a composite layer 100 for connecting the perovskite top cell 300 and the crystalline silicon bottom cell 200.

[0045] The perovskite top solar cell 300 includes a composite hole transport layer 310, which includes a first hole transport layer 310a and a second hole transport layer 310b, wherein the first hole transport layer 310a is in contact with the composite layer 100.

[0046] The first hole transport layer 310a is obtained by sputtering a nickel oxide target with H2 in an oxygen-free sputtering atmosphere, and the second hole transport layer 310b is obtained by sputtering a nickel oxide target in a hydrogen-free atmosphere.

[0047] Currently, most perovskite / crystalline silicon tandem solar cells use a single-layer hole transport layer. This single-layer layer struggles to achieve rapid extraction and collection of hole carriers while simultaneously maintaining good contact with the recombination layer for rapid hole transport, thus limiting further improvements in device efficiency. Therefore, new processing techniques are needed to enable the hole transport layer to extract and collect charge carriers, improve the contact between the hole transport layer and the recombination layer, reduce the contact potential difference and contact resistance, and ultimately enhance the cell's photoelectric conversion efficiency.

[0048] To overcome the defects of the single hole transport layer mentioned above, this application provides a perovskite / crystalline silicon tandem solar cell. The perovskite / crystalline silicon tandem solar cell connects the perovskite top cell 300 and the crystalline silicon bottom cell 200 in series through a composite layer 100. The perovskite top cell 300 includes a composite hole transport layer 310, which includes a first hole transport layer 310a and a second hole transport layer 310b. The first hole transport layer 310a is obtained by sputtering a nickel oxide target with H2 in an oxygen-free sputtering atmosphere. This first hole transport layer 310a can reduce interface defects, achieve energy level matching, improve interface contact characteristics, and enhance carrier transport at the interface. The second hole transport layer 310b is obtained by sputtering a nickel oxide target in a hydrogen-free atmosphere. This second hole transport layer 310b serves as a carrier extraction and collection layer, which can quickly extract and collect hole carriers generated by the perovskite light-absorbing layer 330. With a higher carrier concentration, a larger built-in electric field is obtained in the perovskite top cell 300. At the same time, the high carrier concentration can achieve higher conductivity and reduce the overall series resistance of the device.

[0049] In some alternative embodiments, the composite hole transport layer 310 is a bilayer NiO composed of a first hole transport layer 310a and a second hole transport layer 310b. x Thin film, bilayer NiO x The thickness of the thin film is 11nm-25nm.

[0050] For example, bilayer NiO x The thickness of the thin film can be 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, 25nm, and any other value between 11nm and 25nm.

[0051] In some alternative implementations, the thickness of the first hole transport layer 310a is 1 nm to 5 nm.

[0052] For example, the thickness of the first hole transport layer 310a can be 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm, and any other value between 1 nm and 5 nm.

[0053] In some alternative implementations, the thickness of the second hole transport layer 310b is 10nm-20nm.

[0054] For example, the thickness of the second hole transport layer 310b can be 10nm, 10.5nm, 11nm, 11.5nm, 12nm, 12.5nm, 13nm, 13.5nm, 14nm, 14.5nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, and any other value between 10nm and 20nm.

[0055] In some alternative implementations, the carrier concentration of the first hole transport layer 310a is 1.0 × 10⁻⁶. 17 / cm 3 -6.0×10 18 / cm 3 The carrier mobility is 0.4 cm⁻¹ 2 / Vs-6.0cm 2 / Vs, resistivity 2.6 ohm.cm-10.5 ohm.cm.

[0056] For example, the carrier concentration of the first hole transport layer 310a can be 1.0 × 10⁻⁶. 17 / cm 3 2.0×10 17 / cm 3 3.0×10 17 / cm3 4.0×10 17 / cm 3 5.0×10 17 / cm 3 6.0×10 17 / cm 3 1.0×10 18 / cm 3 2.0×10 18 / cm 3 3.0×10 18 / cm 3 4.0×10 18 / cm 3 5.0×10 18 / cm 3 6.0×10 18 / cm 3 and 1.0×10 17 / cm 3 -6.0×10 18 / cm 3 Any other value between these ranges. The carrier mobility can be 0.4 cm⁻¹. 2 / Vs、1.0cm 2 / Vs、2.0cm 2 / Vs、3.0cm 2 / Vs、4.0cm 2 / Vs、5.0cm 2 / Vs、6.0cm 2 / Vs and 0.4cm 2 / Vs-6.0cm 2 Any other value between / Vs. The resistivity can be 2.6 ohm.cm, 3.0 ohm.cm, 4.0 ohm.cm, 5.0 ohm.cm, 6.0 ohm.cm, 7.0 ohm.cm, 8.0 ohm.cm, 9.0 ohm.cm, 10.0 ohm.cm, 10.56 ohm.cm, and any other value between 2.6 and 10.5 ohm.cm.

[0057] In some alternative implementations, the carrier concentration of the second hole transport layer 310b is 9.0 × 10⁻⁶. 18 / cm 3 -5.0×10 20 / cm 3 The carrier mobility is 0.01 cm⁻¹ 2 / Vs-0.3cm 2 / Vs, resistivity is 0.4 ohm.cm-2.5 ohm.cm.

[0058] For example, the carrier concentration of the second hole transport layer 310b can be 9.0 × 10⁻⁶. 18 / cm 3 10.0×10 18 / cm 3 1.0×10 20 / cm 3 2.0×10 20 / cm 3 3.0×10 20 / cm 3 4.0×10 20 / cm 3 5.0×10 20 / cm 3 and 9.0×10 18 / cm 3 -5.0×10 20 / cm 3 Any other value between these ranges. Carrier mobility can be 0.01 cm⁻¹. 2 / Vs、0.1cm 2 / Vs、0.2cm 2 / Vs、0.3cm 2 / Vs and 0.01cm 2 / Vs-0.3cm 2 Any other value between / Vs. Resistivity is 0.4 ohm.cm, 0.5 ohm.cm, 1.0 ohm.cm, 1.5 ohm.cm, 2.0 ohm.cm, 2.5 ohm.cm, and any other value between 0.4 ohm.cm and 2.5 ohm.cm.

[0059] Secondly, embodiments of this application also provide a method for preparing the above-mentioned composite hole transport layer 310, which includes: providing a crystalline silicon base cell 200; preparing a composite layer 100 on the crystalline silicon base cell 200; and preparing a composite hole transport layer 310 on the side of the composite layer away from the crystalline silicon base cell. The step of preparing the composite hole transport layer 310 includes the following steps:

[0060] A first hole transport layer 310a is formed by sputtering using a nickel oxide target in a first atmosphere, wherein the first atmosphere contains argon and hydrogen; then, a second hole transport layer 310b is formed by sputtering using a nickel oxide target on the first hole transport layer 310a in a second atmosphere, wherein the second atmosphere contains argon and optional oxygen.

[0061] In some alternative embodiments, the process conditions for forming the first hole transport layer 310a include: using NiO xAs the target material, the sputtering pressure was controlled at 0.3 Pa-1.0 Pa, the sputtering temperature at 23 °C-200 °C, and the sputtering power at 100 W-1100 W for NiO sputtering. x Film formation.

[0062] In some alternative embodiments, during sputtering, the flow rates of the first atmosphere are controlled as follows: the Ar flow rate into the chamber is controlled to be 500 sccm-1200 sccm, the O2 flow rate is 0 sccm, and the H2 flow rate is 0.1%-3% of the Ar flow rate.

[0063] For example, the Ar flow rate introduced into the chamber can be any value between 500 sccm, 600 sccm, 700 sccm, 800 sccm, 900 sccm, 1000 sccm, 1100 sccm, 1200 sccm, and 500 sccm-1200 sccm; the O2 flow rate is 0 sccm; the H2 flow rate can be any value between 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, and 0.1%-3% of the Ar flow rate; and the sputtering pressure can be 0.3 P. a. 0.4Pa, 0.5Pa, 0.6Pa, 0.7Pa, 0.8Pa, 0.9Pa, 1.0Pa, and any other value between 0.3Pa and 1.0Pa; the sputtering temperature can be 23℃, 50℃, 100℃, 150℃, 200℃, and any other value between 23℃ and 200℃; the sputtering power can be 100W, 200W, 300W, 400W, 500W, 600W, 700W, 800W, 900W, 100W, 1100W, and any other value between 100W and 1100W.

[0064] In some alternative embodiments, the process conditions for forming the second hole transport layer 310b include: using NiO x As the target material, the sputtering pressure was controlled at 0.3 Pa-1.0 Pa, the sputtering temperature at 23 °C-200 °C, and the sputtering power at 100 W-1100 W for NiO sputtering. x Film formation.

[0065] In some alternative implementations, during sputtering, the flow rates of the second atmosphere are controlled as follows: the Ar flow rate is controlled at 500 sccm-1200 sccm, the O2 flow rate is controlled at 0 sccm-10 sccm, and the H2 flow rate is controlled at 0 sccm.

[0066] For example, the Ar flow rate introduced into the chamber can be any other value between 500 sccm, 600 sccm, 700 sccm, 800 sccm, 900 sccm, 1000 sccm, 1100 sccm, 1200 sccm, and 500 sccm-1200 sccm; the O2 flow rate can be any other value between 0 sccm, 1 sccm, 2 sccm, 3 sccm, 4 sccm, 5 sccm, 6 sccm, 7 sccm, 8 sccm, 9 sccm, 10 sccm, and 0 sccm-10 sccm; and the H2 flow rate is 0. The sputtering pressure can be any other value between 0.3Pa, 0.4Pa, 0.5Pa, 0.6Pa, 0.7Pa, 0.8Pa, 0.9Pa, 1.0Pa, and 0.3Pa-1.0Pa; the sputtering temperature can be any other value between 23℃, 50℃, 100℃, 150℃, 200℃, and 23℃-200℃; and the sputtering power can be any other value between 100W, 200W, 300W, 400W, 500W, 600W, 700W, 800W, 900W, 100W, 1100W, and 100W-1100W.

[0067] Thirdly, embodiments of this application also provide a perovskite / crystalline silicon tandem solar cell, including: a perovskite top cell 300 and a crystalline silicon bottom cell 200, and a composite layer 100 for connecting the perovskite top cell 300 and the crystalline silicon bottom cell 200.

[0068] The perovskite top solar cell 300 includes a composite hole transport layer 310, which includes a first hole transport layer 310a and a second hole transport layer 310b, wherein the first hole transport layer 310a is in contact with the composite layer 100.

[0069] The first hole transport layer 310a and the second hole transport layer 310b are prepared using the above-described preparation method.

[0070] This application also provides a perovskite / crystalline silicon tandem solar cell, comprising: a perovskite top cell 300, a crystalline silicon bottom cell 200, and a composite layer 100 connecting the perovskite top cell 300 and the crystalline silicon bottom cell 200. The perovskite top cell 300 includes a composite hole transport layer 310, which includes a first hole transport layer 310a and a second hole transport layer 310b. The first hole transport layer 310a is in contact with the composite layer 100. The first hole transport layer 310a in the composite hole transport layer 310 can increase charge transport at the interface with the composite layer. The second hole transport layer 310b serves as a carrier extraction and collection layer, which can quickly extract and collect hole carriers generated by the perovskite light-absorbing layer, thereby achieving higher conductivity of NiOx and reducing the overall series resistance of the device.

[0071] In some embodiments of this application, a hole modification layer 320 and a passivation layer 340 are also included. The hole modification layer 320 is located between the second hole transport layer 310b and the perovskite light-absorbing layer 330, and the passivation layer 340 is located between the perovskite light-absorbing layer 330 and the electron transport layer 350.

[0072] In some embodiments of this application, it further includes: a buffer layer 360, a second transparent conductive oxide layer 370, and an optical antireflection layer 380 stacked on the front side of the electron transport layer 350.

[0073] In some embodiments of this application, the crystalline silicon bottom cell 200 includes an N-type silicon wafer 240, a second intrinsic amorphous silicon layer 250 and an N-type doped nanocrystalline silicon layer 260 sequentially disposed on the front side of the N-type silicon wafer 240, and a first intrinsic amorphous silicon layer 230, a P-type doped nanocrystalline silicon layer 220 and a first transparent conductive oxide layer 210 sequentially disposed on the back side of the N-type silicon wafer 240.

[0074] In some embodiments of this application, the battery further includes: a first grid electrode 410 and a second grid electrode 420. The second grid electrode 420 is disposed on the surface of the perovskite / crystalline silicon tandem solar cell away from the crystalline silicon bottom cell 200. The second grid electrode 420 penetrates the optical antireflection layer 380 and contacts the second transparent conductive oxide layer 370 to form the positive electrode of the battery. The first grid electrode 410 is disposed on the surface of the perovskite / crystalline silicon tandem solar cell away from the perovskite top cell 300. The first grid electrode 410 contacts the first transparent conductive oxide layer 210 to form the negative electrode of the battery.

[0075] Fourthly, this application also provides a perovskite / crystalline silicon tandem solar cell, comprising: a perovskite top cell 300, a crystalline silicon bottom cell 200, and a composite layer 100 for connecting the perovskite top cell 300 and the crystalline silicon bottom cell 200, a first grid electrode 410 and a second grid electrode 420; the perovskite top cell 300 includes a first hole transport layer 310a, a second hole transport layer 310b, a hole modification layer 320, a perovskite light-absorbing layer 330, a passivation layer 340, an electron transport layer 350, a buffer layer 360, and a second hole transport layer 420, sequentially disposed on the front side of the composite layer 100. Two transparent conductive oxide layers 370 and an optical anti-reflection layer 380 are present. A second gate electrode 420 penetrates the optical anti-reflection layer 380 and contacts the second transparent conductive oxide layer 370 to form the positive electrode of the battery. The crystalline silicon bottom battery 300 includes an N-type doped nanocrystalline silicon layer 260, a second intrinsic amorphous silicon layer 250, an N-type silicon wafer 240, a first intrinsic amorphous silicon layer 230, a P-type doped nanocrystalline silicon layer 220 and a first transparent conductive oxide layer 210, which are sequentially disposed on the back side of the composite layer 100. A first gate electrode 410 contacts the first transparent conductive oxide layer 210 to form the negative electrode of the battery.

[0076] Fifthly, this application also provides a photovoltaic module, including the aforementioned perovskite / crystalline silicon tandem solar cell.

[0077] The present application will be further described below with reference to embodiments.

[0078] The perovskite / crystalline silicon tandem solar cell provided in this application embodiment includes: a perovskite top cell 300, a crystalline silicon bottom cell 200, and a composite layer 100 connecting the perovskite top cell and the crystalline silicon bottom cell. The perovskite top cell 300 includes a first hole transport layer 310a, a second hole transport layer 310b, a hole modification layer 320, a perovskite light-absorbing layer 330, a passivation layer 340, an electron transport layer 350, a buffer layer 360, a second transparent conductive oxide layer 370, and an optical anti-reflection layer, all sequentially disposed on the composite layer 100. The crystalline silicon base cell 200 includes an N-type silicon wafer 240, and a second intrinsic amorphous silicon layer 250 and an N-type doped nanocrystalline silicon layer 260 sequentially disposed on the front side of the N-type silicon wafer 240, and a first intrinsic amorphous silicon layer 230, a P-type doped nanocrystalline silicon layer 220 and a first transparent conductive oxide layer 210 sequentially disposed on the back side of the N-type silicon wafer 240. The first transparent conductive oxide layer 210 forms an ohmic contact with the first gate electrode 410, and the optical antireflection layer 380 forms an ohmic contact with the second gate electrode 420.

[0079] The above method for fabricating perovskite / crystalline silicon tandem solar cells includes the following steps:

[0080] (1) A second intrinsic amorphous silicon layer 250 is prepared on the receiving side of the N-type silicon wafer 240 and a first intrinsic amorphous silicon layer 230 is prepared on the back side;

[0081] (2) An N-type doped nanocrystalline silicon layer 260 is prepared on the second intrinsic amorphous silicon layer 250 on the receiving side of the N-type silicon wafer 240, and a P-type doped nanocrystalline silicon layer 220 is prepared on the first intrinsic amorphous silicon layer 230 on the back side of the N-type silicon wafer 240.

[0082] (3) A first transparent conductive oxide layer 210 is prepared on a P-type doped nanocrystalline silicon layer 220 by DC / RF magnetron sputtering process;

[0083] (4) A composite layer 100 is prepared on the N-type doped nanocrystalline silicon layer 260;

[0084] (5) A first hole transport layer 310a is prepared on the composite layer 100;

[0085] (6) A second hole transport layer 310b is prepared on the first hole transport layer 310a;

[0086] (7) A hole modification layer 320 is prepared on the second hole transport layer 310b;

[0087] (8) A perovskite light-absorbing layer 330 is prepared on the front hole modification layer 320;

[0088] (9) A passivation layer 340 is prepared on the perovskite light-absorbing layer 330 on the front side;

[0089] (10) An electron transport layer 350 is prepared on the front passivation layer 340;

[0090] (11) A buffer layer 360 is prepared on the front electron transport layer 350;

[0091] (12) A second transparent conductive oxide layer 370 is prepared on the buffer layer 360 by DC / RF magnetron sputtering process;

[0092] (13) An optical anti-reflection layer 380 is prepared on the second transparent conductive oxide layer 370;

[0093] (14) A second gate electrode 420 is fabricated on the front optical antireflection layer 380, and a first gate electrode 410 is fabricated on the back first transparent conductive oxide layer 210.

[0094] It should be noted that the fabrication method of the second gate electrode 420 is as follows: A metal, such as an Ag electrode, is deposited on the second transparent conductive oxide layer 370. Then, an optical antireflection layer 380 is deposited using metal evaporation. During the evaporation process, the Ag electrode is shielded to prevent the optical antireflection layer 380 from depositing onto the Ag electrode. Alternatively, the optical antireflection layer 380 can be deposited first, thus partially shielding the second transparent conductive oxide layer 370. Then, the Ag electrode is fabricated in the area shielded by the optical antireflection layer 380, so that the Ag electrode is in contact with the second transparent conductive oxide layer 370.

[0095] Example 1

[0096] A perovskite / crystalline silicon tandem solar cell includes a composite hole transport layer 310 comprising a first hole transport layer 310a disposed on the composite layer 100 of the perovskite / crystalline silicon tandem solar cell and a second hole transport layer 310b stacked on the first hole transport layer 310a. The method for fabricating the composite hole transport layer 310 is as follows:

[0097] (1) First hole transport layer 310a:

[0098] The first hole transport layer was prepared by radio frequency sputtering, and the sputtering process was as follows: NiO was used. x The sputtering target was controlled at a pressure of 0.50 Pa, a sputtering temperature of 23 °C, an Ar flow rate of 700 sccm, an O2 flow rate of 0 sccm, and an H2 flow rate of 2.0% of the Ar flow rate. The sputtering power was 900 W. The thickness of the first hole transport layer was 3 nm, and the carrier concentration was 5.5 × 10⁻⁶.17 / cm 3 The carrier mobility is 3.8 cm⁻¹ 2 / Vs, resistivity 2.99 ohm.cm.

[0099] (2) Second hole transport layer 310b:

[0100] The second hole transport layer was fabricated using radio frequency sputtering. The sputtering process was as follows: sputtering pressure was 0.5 Pa, sputtering temperature was 23 °C, Ar flow rate was 700 sccm, O2 flow rate was 0 sccm, H2 flow rate was 0 sccm, and sputtering power was 900 W. The resulting second hole transport layer had a thickness of 15 nm and a carrier concentration of 9.9 × 10⁻⁶. 18 / cm 3 The carrier mobility is 0.26 cm⁻¹ 2 / Vs, resistivity is 2.42 ohm·cm.

[0101] Comparative Example 1

[0102] The hole transport layer uses a single film layer, made of NiO. x The target material was prepared using radio frequency sputtering. The sputtering conditions were: sputtering pressure of 0.50 Pa, sputtering temperature of 23 °C, Ar flow rate of 700 sccm, O2 flow rate of 0 sccm, and sputtering power of 900 W. Using this hole transport layer, a NiOx film with a thickness of 18 nm was fabricated, and the measured carrier concentration was 9.8 × 10⁻⁶. 18 / cm 3 The carrier mobility is 0.28 cm⁻¹ 2 / Vs.

[0103] Comparative Example 2

[0104] The hole transport layer uses a single film layer, made of NiO. x The target material was prepared using radio frequency sputtering. The sputtering conditions were: sputtering pressure of 0.50 Pa, sputtering temperature of 23℃, Ar flow rate of 700 sccm, O2 flow rate of 3 sccm, and sputtering power of 900 W. Using this hole transport layer, a NiOx thin film with a thickness of 18 nm was fabricated, and the measured carrier concentration was 7.6 × 10⁻⁶. 19 / cm 3 The carrier mobility is 0.15 cm⁻¹ 2 / Vs.

[0105] Comparative Example 3

[0106] The hole transport layer uses a single film layer, made of NiO. xThe target material was prepared using radio frequency (RF) sputtering. The sputtering conditions were: RF magnetron sputtering with a sputtering pressure of 0.50 Pa, a sputtering temperature of 23 °C, an Ar flow rate of 700 sccm, an O2 flow rate of 5 sccm, and a sputtering power of 900 W. Using this hole transport layer, a NiOx thin film with a thickness of 18 nm was fabricated, and the measured carrier concentration was 1.6 × 10⁻⁶. 20 / cm 3 The carrier mobility is 0.09 cm⁻¹ 2 / Vs.

[0107] Comparative Example 4

[0108] The hole transport layer uses a single film layer, made of NiO. x The target material was fabricated using radio frequency sputtering. The sputtering conditions were as follows: radio frequency magnetron sputtering, sputtering pressure of 0.20 Pa, sputtering temperature of 220 °C, Ar flow rate of 300 sccm, O2 flow rate of 3 sccm, and sputtering power of 1200 W. Using this hole transport layer, a NiOx thin film with a thickness of 18 nm was obtained.

[0109] Comparative Example 5

[0110] The hole transport layer uses a single film layer, made of NiO. x The target material was fabricated using radio frequency sputtering. The sputtering conditions were as follows: radio frequency magnetron sputtering, sputtering pressure of 1.1 Pa, sputtering temperature of 20 °C, Ar flow rate of 1500 sccm, O2 flow rate of 3 sccm, and sputtering power of 50 W. Using this hole transport layer, a NiOx thin film with a thickness of 18 nm was obtained.

[0111] The preparation parameters for each comparative example and embodiment are shown in Table 1.

[0112] Table 1

[0113]

[0114] The Wavelabs solar simulator is used to test the performance of photovoltaic devices (including solar cells and perovskite cells), such as open-circuit voltage, short-circuit current density, fill factor, and energy conversion efficiency. The Wavelabs simulator, along with electronic loads, data acquisition and computing equipment, is used to test the electrical performance of photovoltaic devices, such as PCE, Voc, and J. SC Parameters such as PCE and FF are used to reflect the performance of the above perovskite / crystalline silicon tandem solar cells. PCE represents power conversion efficiency (%), Voc represents open-circuit voltage (V), and Jsc represents short-circuit current density (mA / cm²). 2FF represents the fill factor, expressed as a percentage. See Table 2 for detailed experimental results.

[0115] Table 2

[0116]

[0117]

[0118] As can be seen from the test results in Table 2, comparing the test results of Examples 1-10 with those of Comparative Examples 1-3, it can be seen that the photoelectric conversion efficiency of the solar cells in Comparative Examples 1-3 is relatively low. This may be because the hole transport layer in the comparative examples is a single-layer structure with a single NiO layer. x To balance the interfacial contact with the composite layer and the extraction and collection of its own holes, the film layer can only be optimized to obtain a relatively optimal overall film layer (i.e., under comprehensive conditions, only an intermediate value can be selected for the optimal overall performance of the solar cell). Using a single NiO layer... x In the film layer, the hole transport layer is difficult to achieve contact matching with the composite layer, resulting in hindered interfacial charge transfer; simultaneously, the NiO in contact with the composite layer... x Surface interface defects cause recombination losses. Simultaneously, a single-layer hole transport layer struggles to achieve rapid extraction and collection of hole carriers. This limits further improvements in the device's flyback effect (FF), Voc, and efficiency. The perovskite / crystalline silicon tandem solar cell provided in this application employs a composite hole transport layer. During the fabrication of the first hole transport layer, H2 is introduced to transport high-valence Ni... 3+ Ni4 + Reduced to low-cost Ni 2+ Meanwhile, H + As a shallow donor impurity, it can donate electrons, reducing the hole carrier concentration, and has a low work function, enabling energy level matching with the intermediate recombination layer. NiO reduced by H₂ x Thin films possess high carrier mobility, enabling rapid interfacial charge transport; simultaneously, H + It can passivate NiO x To address the defects of the first hole transport layer and reduce recombination losses during hole transport, the second hole transport layer is fabricated by introducing O2, resulting in a higher hole carrier concentration and a larger built-in electric field compared to Comparative Example 2. This allows for rapid extraction and collection of hole carriers generated by the perovskite light-absorbing layer. Simultaneously, the second hole transport layer exhibits lower resistivity compared to the first hole transport layer and Comparative Example 2, reducing the overall series resistance of the device. The photoelectric conversion efficiency of the solar cells in Examples 1-10 of this application is significantly improved compared to Comparative Examples 1, 2, and 3, indicating that the solar cells with the hole transport layer structure provided in these examples possess excellent photoelectric conversion performance.

[0119] Furthermore, the test results of Comparative Examples 4 and 5 show that excessively low Ar flow rates result in low chamber process pressure, while excessively high sputtering power leads to particles with high energy, causing bombardment damage to the composite film on the front surface and resulting in defects. Excessively high Ar flow rates result in low chamber process pressure, and excessively low sputtering power both lead to low particle energy, which is detrimental to the thermal motion of particles during film formation, leading to an increase in film defects. Excessively low chamber temperatures result in low silicon substrate temperatures, which is detrimental to film crystallization, leading to an increase in film defects. Excessively high temperatures cause the H-bonds in the crystalline silicon film of the crystalline silicon bottom cell to break, reducing passivation performance.

[0120] The test results from Examples 1-4 show that, by optimizing the O2 flux in the preparation of the second hole transport layer, the embodiments of this application can obtain NiO with optimal low resistivity. x Thin films can reduce the overall series resistance of devices. This is in contrast to single NiO films, which are used to balance the interfacial contact with the composite layer and the extraction and collection of their own holes. x The film layer has a lower resistivity. Furthermore, compared to single NiO, it exhibits lower resistivity. x The membrane layer has a higher carrier concentration, which can result in a larger built-in electric field.

[0121] The test results from Examples 3, 5, and 6 show that by optimizing the H2 flux ratio in the preparation of the first hole transport layer, this application can obtain high-quality NiO with better contact with the composite layer and lower defects. x Thin films are beneficial for improving device performance. However, excessively low H2 flow rates are detrimental to NiO. x The modification of the thin film is limited, making it difficult to achieve the desired effect. While excessively high H2 flow rates can improve contact with the composite film, excessively low carrier concentrations can lead to problems with NiO. x The high resistivity of thin films can cause device efficiency to decrease.

[0122] The test results from Examples 3 and 7-10 show that the first hole transport layer has high resistivity and is not suitable for a high thickness, as a high thickness will increase the series resistance of the device. However, it should not be too thin either, as an excessively thin layer will result in insufficient coverage on the composite layer, significantly reducing the contact effect. The second hole transport layer has a high carrier concentration, and as it is used for hole extraction and transport, it needs a certain thickness. Too little thickness is not conducive to hole extraction and transport, while too much thickness will result in an excessively thick overall film, which will also increase the series resistance of the device. Overall, by adjusting the thickness of the first hole transport layer to 1nm-5nm and the thickness of the second hole transport layer to 10nm-20nm, the first hole transport layer is made thinner than the second hole transport layer. This achieves better energy level matching with the composite layer while also obtaining low resistivity and excellent charge extraction and transport capabilities.

[0123] In summary, the solutions provided in this application optimize the fabrication processes of the first and second hole transport layers, thereby obtaining a composite hole transport layer with lower interface loss and higher film quality, which is beneficial to improving the photoelectric conversion efficiency of solar cells.

[0124] The above are merely preferred embodiments of this application and are not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A perovskite / crystalline silicon tandem solar cell, characterized in that, include: Perovskite top cell and crystalline silicon bottom cell, and a composite layer for connecting the perovskite top cell and the crystalline silicon bottom cell; The perovskite top solar cell includes a composite hole transport layer, which includes a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is in contact with the composite layer. The first hole transport layer is obtained by sputtering a nickel oxide target with H2 in an oxygen-free sputtering atmosphere, and the second hole transport layer is obtained by sputtering a nickel oxide target in a hydrogen-free atmosphere.

2. The perovskite / crystalline silicon tandem solar cell according to claim 1, characterized in that, The composite hole transport layer is a double-layer NiO composed of a first hole transport layer and a second hole transport layer. x Thin film, the bilayer NiO x The thickness of the thin film is 11nm-25nm.

3. The perovskite / crystalline silicon tandem solar cell according to claim 2, characterized in that, The thickness of the first hole transport layer is 1nm-5nm.

4. The perovskite / crystalline silicon tandem solar cell according to claim 2, characterized in that, The thickness of the second hole transport layer is 10nm-20nm.

5. The perovskite / crystalline silicon tandem solar cell according to claim 1, characterized in that, The carrier concentration of the first hole transport layer is 1.0 × 10⁻⁶. 17 / cm 3 -6.0×10 18 / cm 3 The carrier mobility is 0.4 cm⁻¹ 2 / Vs-6.0cm 2 / Vs, resistivity 2.6 ohm.cm-10.5 ohm.cm.

6. The perovskite / crystalline silicon tandem solar cell according to claim 1, characterized in that, The carrier concentration of the second hole transport layer is 9.0 × 10⁻⁶. 18 / cm 3 -5.0×10 20 / cm 3 The carrier mobility is 0.01 cm⁻¹ 2 / Vs-0.3cm 2 / V, resistivity is 0.4 ohm·cm-2.5 ohm·cm.

7. A method for preparing a perovskite / crystalline silicon tandem solar cell according to any one of claims 1-6, characterized in that, It includes: Provides crystalline silicon base cells; A composite layer is prepared on the crystalline silicon substrate cell; A composite hole transport layer is fabricated on the side of the composite layer away from the crystalline silicon substrate. The process of fabricating the composite hole transport layer includes the following steps: A first hole transport layer is formed by sputtering using a nickel oxide target in a first atmosphere, wherein the first atmosphere contains argon and hydrogen; then, a second hole transport layer is formed by sputtering using a nickel oxide target in a second atmosphere, wherein the second atmosphere contains argon and optional oxygen.

8. The preparation method according to claim 7, characterized in that, The process conditions for forming the first hole transport layer include: using NiO x As the target material, the sputtering pressure was controlled at 0.3 Pa-1.0 Pa, the sputtering temperature at 23 °C-200 °C, and the sputtering power at 100 W-1100 W for NiO sputtering. x Film formation.

9. The preparation method according to claim 8, characterized in that, During the sputtering process, the flow rates of the first atmosphere are controlled as follows: the flow rate of Ar introduced into the chamber is controlled to be 500 sccm-1200 sccm, the flow rate of O2 is 0 sccm, and the flow rate of H2 is 0.1%-3% of the flow rate of Ar.

10. The preparation method according to claim 7, characterized in that, The process conditions for forming the second hole transport layer include: using NiO x As the target material, the sputtering pressure was controlled at 0.3 Pa-1.0 Pa, the sputtering temperature at 23 °C-200 °C, and the sputtering power at 100 W-1100 W for NiO sputtering. x Film formation.

11. The preparation method according to claim 10, characterized in that, During the sputtering process, the flow rates of the second atmosphere are controlled as follows: the flow rate of Ar entering the chamber is controlled to be 500 sccm-1200 sccm, the flow rate of O2 is 0 sccm-10 sccm, and the flow rate of H2 is 0 sccm.

12. A perovskite / crystalline silicon tandem solar cell, characterized in that, include: Perovskite top cell and crystalline silicon bottom cell, and a composite layer for connecting the perovskite top cell and the crystalline silicon bottom cell; The perovskite top solar cell includes a hole transport layer, which includes a first hole transport layer and a second hole transport layer, wherein the first hole transport layer is in contact with the composite layer. The first hole transport layer and the second hole transport layer are prepared by the preparation method described in any one of claims 7-11.

13. The perovskite / crystalline silicon tandem solar cell according to claim 12, characterized in that, Also includes: A hole-modifying layer and a passivation layer are provided, wherein the hole-modifying layer is located between the second hole transport layer and the perovskite light-absorbing layer, and the passivation layer is located between the perovskite light-absorbing layer and the electron transport layer.

14. The perovskite / crystalline silicon tandem solar cell according to claim 13, characterized in that, Also includes: A buffer layer, a second transparent conductive oxide layer, and an optical antireflection layer are stacked on the front side of the electron transport layer.

15. The perovskite / crystalline silicon tandem solar cell according to claim 12, characterized in that, The crystalline silicon bottom cell includes an N-type silicon wafer, and a second intrinsic amorphous silicon layer and an N-type doped nanocrystalline silicon layer sequentially disposed on the front side of the N-type silicon wafer, and a first intrinsic amorphous silicon layer, a P-type doped nanocrystalline silicon layer and a first transparent conductive oxide layer sequentially disposed on the back side of the N-type silicon wafer.

16. The perovskite / crystalline silicon tandem solar cell according to claim 12, characterized in that, Also includes: A first grid electrode and a second grid electrode are disposed on the surface of the perovskite / crystalline silicon tandem solar cell away from the crystalline silicon bottom cell. The second grid electrode penetrates the optical antireflection layer and contacts the second transparent conductive oxide layer to form the positive electrode of the cell. The first grid electrode is disposed on the surface of the perovskite / crystalline silicon tandem solar cell away from the perovskite top cell. The first grid electrode contacts the first transparent conductive oxide layer to form the negative electrode of the cell.

17. A perovskite / crystalline silicon tandem solar cell, characterized in that, include: A perovskite top-mounted solar cell and a crystalline silicon bottom-mounted solar cell, and a composite layer for connecting the perovskite top-mounted solar cell and the crystalline silicon bottom-mounted solar cell, a first grid electrode and a second grid electrode; the perovskite top-mounted solar cell includes a first hole transport layer, a second hole transport layer, a hole modification layer, a perovskite light-absorbing layer, a passivation layer, an electron transport layer, a buffer layer, a second transparent conductive oxide layer and an optical anti-reflection layer sequentially disposed on the front side of the composite layer, the second grid electrode penetrating the optical anti-reflection layer and contacting the second transparent conductive oxide layer to form the positive electrode of the cell; the crystalline silicon bottom-mounted solar cell includes an N-type doped nanocrystalline silicon layer, a second intrinsic amorphous silicon layer, an N-type silicon wafer, a first intrinsic amorphous silicon layer, a P-type doped nanocrystalline silicon layer and a first transparent conductive oxide layer sequentially disposed on the back side of the composite layer, the first grid electrode contacting the first transparent conductive oxide layer to form the negative electrode of the cell.

18. A photovoltaic module, characterized in that, include: The perovskite / crystalline silicon tandem solar cell of claim 1, or the perovskite / crystalline silicon tandem solar cell prepared by the preparation method of claim 7, or the perovskite / crystalline silicon tandem solar cell of claim 12, or the perovskite / crystalline silicon tandem solar cell of claim 17.

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