Silicon-based-perovskite laminated photovoltaic device and preparation method thereof

Abstract

The invention discloses a silicon-based-perovskite laminated photovoltaic device and a preparation method thereof, and relates to the technical field of photovoltaic devices. The photovoltaic device structure comprises a silicon cell structure and a perovskite cell structure which are connected with each other. The silicon cell structure comprises a crystalline silicon substrate, and a first amorphous silicon intrinsic film, a p-type amorphous silicon film, an ITO layer and a silver layer are sequentially arranged on one side of the crystalline silicon substrate. A second amorphous silicon intrinsic film, an n-type amorphous silicon film and an anode layer are sequentially arranged outside the other side of the substrate; the perovskite cell structure comprises a perovskite layer, and one side of the perovskite layer is sequentially provided with a first interface modification layer and a hole transport layer. A second interface modification layer, an electron transport layer, a buffer layer, a window layer, a cathode layer and an anti-reflection layer are sequentially arranged on the other side of the substrate; the anode layer is connected to the hole transport layer. The photoelectric conversion efficiency is high, and the device stability is strong; meanwhile, the structure is simple, integration is easy, environment friendliness is achieved, and wide application and popularization prospects are achieved.

Description

Technical Field

[0001] The present application relates to the technical field of photovoltaic devices, and in particular to a silicon-based perovskite stacked photovoltaic device and a preparation method thereof. Background Art

[0002] With the increasing global energy demand and the general enhancement of environmental protection awareness, the development of efficient and stable solar cell technology has become the focus of global scientific research and industry. Traditional silicon-based solar cells have long dominated the photovoltaic market with their excellent photoelectric conversion efficiency and long-term stability. However, with the advancement of science and technology, the photoelectric conversion efficiency of silicon-based solar cells has gradually approached its theoretical limit, and it is becoming increasingly difficult to further improve it.

[0003] At the same time, as an emerging photovoltaic technology, perovskite solar cells have rapidly attracted widespread attention worldwide with their advantages such as high efficiency, low cost and easy large-scale preparation. Perovskite materials have excellent photoelectric properties and can achieve higher photoelectric conversion efficiency than traditional silicon-based solar cells. However, the stability of perovskite solar cells under environmental conditions such as humidity, temperature and light, especially its photodegradation and ion migration, has become the main bottleneck restricting its commercial application.

[0004] In order to overcome the limitations of a single type of solar cell, researchers have proposed an innovative idea of ​​connecting silicon-based solar cells and perovskite solar cells in series, aiming to achieve complementary advantages of the two cells through a stacked structure. This series structure can fully utilize the advantages of silicon-based solar cells in terms of stability, while giving full play to the potential of perovskite solar cells in terms of photoelectric conversion efficiency. However, although the series structure has significant advantages in theory, it still faces many technical challenges in practical applications. For example, interface recombination loss: In the series structure of silicon-based and perovskite solar cells, recombination centers are easily formed at the interface between the two materials, resulting in the recombination of photogenerated carriers at the interface, thereby reducing the photoelectric conversion efficiency. Low carrier transmission efficiency: Due to the difference in the band structure of silicon-based and perovskite materials, carriers are easily hindered during the transmission process between the two materials, resulting in low transmission efficiency; stability issues: Perovskite materials have poor stability under environmental conditions such as humidity, temperature and light, and are prone to photodegradation and ion migration, resulting in decreased battery performance. These problems have become key factors restricting the development of silicon-based and perovskite solar cell series technology. Therefore, how to effectively solve these problems has become a hot spot and difficulty in current research. Summary of the invention

[0005] The purpose of the present application is to provide a silicon-based perovskite stacked photovoltaic device and a preparation method thereof, which has high photoelectric conversion efficiency and strong device stability; at the same time, it has a simple structure, is easy to integrate, is environmentally friendly, and has broad prospects for promotion and application.

[0006] The technical solution of this application is as follows:

[0007] The embodiment of the present application provides a silicon-based perovskite stacked photovoltaic device, which includes a silicon cell structure and a perovskite cell structure connected to each other;

[0008] The silicon cell structure comprises a crystalline silicon substrate, one side of which is provided with a first amorphous silicon intrinsic film, a p-type amorphous silicon film, an ITO layer and a silver layer in sequence; the other side of the crystalline silicon substrate is provided with a second amorphous silicon intrinsic film, an n-type amorphous silicon film and an anode layer in sequence;

[0009] The perovskite battery structure comprises a perovskite layer, one side of the perovskite layer is provided with a first interface modification layer and a hole transport layer in sequence; the other side of the perovskite layer is provided with a second interface modification layer, an electron transport layer, a buffer layer, a window layer, a cathode layer and an anti-reflection layer in sequence;

[0010] The anode layer is connected to the hole transport layer.

[0011] Furthermore, in some embodiments of the present application, the first interface modification layer is prepared from a self-assembled layer material SAM1.

[0012] Furthermore, in some embodiments of the present application, the self-assembly layer material SAM1 includes any one or more of the following materials:

[0013]

[0014]

[0015] Furthermore, in some embodiments of the present application, the second interface modification layer is prepared from a self-assembled layer material SAM2.

[0016] Furthermore, in some embodiments of the present application, the self-assembly layer material SAM2 includes any one or more of the following materials:

[0017]

[0018]

[0019] Furthermore, in some embodiments of the present application, the hole transport layer is nickel oxide (NiO x )layer.

[0020] Furthermore, in some embodiments of the present application, an electron blocking layer and / or an exciton blocking layer is also provided on the nickel oxide layer.

[0021] Furthermore, in some embodiments of the present application, the electron transport layer is C 60 layer.

[0022] Further, in some embodiments of the present application, the above C 60 A hole blocking layer and / or an exciton blocking layer is also arranged on the layer.

[0023] Furthermore, in some embodiments of the present application, the materials of the cathode layer and the anode layer are metals, metal oxides or poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) and modified products thereof.

[0024] Furthermore, in some embodiments of the present application, the metal oxide is any one or more of indium tin oxide, fluorine-doped tin dioxide, zinc oxide and indium gallium zinc oxide.

[0025] Furthermore, in some embodiments of the present application, the above-mentioned metal is aluminum, silver-magnesium alloy, silver or gold.

[0026] The present application also provides a method for preparing the above-mentioned silicon-based perovskite laminated photovoltaic device, which comprises the following steps:

[0027] S1: preparing a crystalline silicon substrate, performing a texture process on one side thereof, and then cleaning the crystalline silicon substrate;

[0028] S2: depositing a first amorphous silicon intrinsic film and a p-type amorphous silicon film in sequence on the textured side of the crystalline silicon substrate by a plasma enhanced chemical vapor deposition process; and depositing a second amorphous silicon intrinsic film and an n-type amorphous silicon film in sequence on the other side of the crystalline silicon substrate;

[0029] S3: preparing an anode layer on the n-type amorphous silicon film by shadow mask sputtering; preparing an ITO layer on the p-type amorphous silicon film by shadow mask sputtering, and then sputtering a silver layer on the ITO layer;

[0030] S4: Annealing the entire material to obtain a silicon cell structure;

[0031] S5: preparing a hole transport layer on the anode layer by solution spin coating, preparing a first interface modification layer on the hole transport layer, and then preparing a perovskite layer on the first interface modification layer by solution processing;

[0032] S6: preparing a second interface modification layer on the perovskite layer, preparing an electron transport layer on the second interface modification layer by thermal evaporation, and preparing a buffer layer on the electron transport layer by atomic deposition technology;

[0033] S7: preparing a window layer on the buffer layer by sputtering, preparing a cathode layer on the window layer by thermal evaporation, and then preparing an anti-reflection layer on the cathode layer to obtain a finished photovoltaic device.

[0034] Compared with the prior art, the embodiments of the present application have at least the following advantages or beneficial effects:

[0035] 1. This application scheme introduces organic self-assembled layer materials (SAM1 and SAM2) as interface modification layers between the perovskite layer and the hole transport layer and the electron transport layer. This design can effectively passivate interface defects, thereby significantly reducing composite losses. This interface passivation technology can not only improve the photoelectric conversion efficiency, but also enhance the stability of the device.

[0036] 2. This application scheme uses high mobility and high stability electron transport materials (C 60 ) and hole transport materials (NiO x ) and optimized their structure and thickness to improve the carrier transport efficiency. This design ensures that photogenerated carriers can be efficiently transferred between the silicon-based and perovskite materials, reducing energy loss.

[0037] 3. This application scheme optimizes the composition and preparation process of perovskite materials to obtain a perovskite light-absorbing layer with high efficiency and stability. It is able to precisely control the crystal structure, doping elements and surface modification of perovskite, thereby improving its ability to resist photodegradation and ion migration.

[0038] 4. This application is based on the existing silicon-based solar cell manufacturing technology and has been innovatively improved. The entire manufacturing process is mature, easy to mass produce, and relatively low in cost, which is conducive to commercial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0040] Figure 1 A schematic diagram of the hierarchical structure of a photovoltaic device provided in an embodiment of the present application;

[0041] Figure 2 This is a current density-voltage characteristic curve of the photovoltaic device of Example 1 of the present application;

[0042] Figure 3This is a current density-voltage characteristic curve of the photovoltaic device of Example 2 of the present application. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0044] It should be noted that relational terms such as "first" and "second" are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the term "comprises" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprises..." do not exclude the existence of other identical elements in the process, method, article or device including its elements.

[0045] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.

[0046] The features and performance of the present application are further described in detail below in conjunction with the embodiments.

[0047] Example 1

[0048] This embodiment provides a silicon-based perovskite stacked photovoltaic device, the overall structure of which is as follows: Figure 1 As shown, it is prepared by the following method:

[0049] S1: Using an n-type double-sided polished floating zone wafer as a crystalline silicon substrate (c-Si), one side of the wafer is textured with potassium hydroxide, and then the crystalline silicon substrate is cleaned with a buffered oxide etching solution;

[0050] S2: On the textured side of the crystalline silicon substrate, a first amorphous silicon intrinsic film [a-Si:H(i)] and a p-type amorphous silicon film [a-Si:H(p)] (thicknesses of 6 nm and 15 nm, respectively) are sequentially deposited by a plasma enhanced chemical vapor deposition process (PECVD); on the other side of the crystalline silicon substrate, a second amorphous silicon intrinsic film [a-Si:H(i)] and an n-type amorphous silicon film [a-Si:H(n)] (thicknesses of 6 nm and 8 nm, respectively) are sequentially deposited;

[0051] S3: Using an In2O3 / SnO2 (ratio of 90 / 10) target, a 20nm thick ITO material is prepared as an anode layer on an n-type amorphous silicon film [a-Si:H(n)] by shadow mask sputtering; a 150nm thick ITO layer is prepared on a p-type amorphous silicon film [a-Si:H(p)] by the same mask method, and then a 200nm thick silver layer is sputtered on the ITO layer;

[0052] S4: annealing the entire material at 200° C. for 20 minutes to obtain a silicon cell structure;

[0053] S5: Prepare a hole transport layer (NiO) on the anode layer by solution spin coating x ) and use the self-assembled material SAM1 (CPA-1 is used in this embodiment) on the hole transport layer ) to prepare a first interface modification layer, and then prepare a perovskite layer on the first interface modification layer by solution processing [FA 0.75 Cs 0.25 Pb(I 0.8 Br 0.2 )3](Perovskite), which is the light absorbing layer;

[0054] S6: Using self-assembled material SAM2 (CPA-7 is used in this example) on the perovskite layer ) to prepare a second interface modification layer, and then prepare a 10 nm thick electron transport layer (C 60 ), and a 6 nm thick buffer layer (SnO2) was prepared on the electron transport layer by atomic deposition technology;

[0055] S7: A 60 nm thick ITO material is prepared on the buffer layer as a window layer by sputtering, and a 25 μm thick cathode layer (Ag) is prepared on the window layer by thermal evaporation, and then a PDMS foil with a negative pyramid texture is used as an anti-reflection layer to obtain a finished photovoltaic device;

[0056] The structure of the photovoltaic device obtained is:

[0057] Ag / ITO / a-Si:H(p) / a-Si:H(i) / c-Si / a-Si:H(i) / a-Si:H(n) / ITO / NiOx / CPA-1 / Perovskite / CPA-7 / C60 / SnO2 / ITO / Ag / PDMS.

[0058] Example 2

[0059] This embodiment is based on Embodiment 1, and differs from Embodiment 1 in that:

[0060] The self-assembly material SAM1 used in this example is CPA-2

[0061] The self-assembly material SAM2 used is CPA-8

[0062] The structure of the photovoltaic device obtained is:

[0063] Ag / ITO / a-Si:H(p) / a-Si:H(i) / c-Si / a-Si:H(i) / a-Si:H(n) / ITO / NiOx / CPA-2 / Perovskite / CPA-8 / C60 / SnO2 / ITO / Ag / PDMS.

[0064] Test example

[0065] The photovoltaic performance of the photovoltaic devices provided in Examples 1 and 2 of the present application was tested:

[0066] The methods of Examples 1 and 2 were used respectively. After the device was prepared, the device was taken out from the evaporation chamber. Then the device was tested in air, and the device current and voltage information was measured by a 2400 power meter produced by Keithley. The device's current density, fill factor, power conversion efficiency and other performance can be calculated from the current, voltage and light intensity information.

[0067] The current density-voltage characteristic curve of the photovoltaic device of Example 1 is as follows: Figure 2 As shown;

[0068] The current density-voltage characteristic curve of the photovoltaic device of Example 2 is as follows: Figure 3 shown.

[0069] It can be seen that the embodiments of the present application can obtain a highly efficient silicon-based-perovskite stacked photovoltaic device.

[0070] In summary, the embodiment of the present application provides a silicon-based perovskite laminated photovoltaic device and a preparation method thereof, and the scheme adopts interface passivation technology, efficient carrier transport layer design and optimized perovskite material, and the product silicon-based perovskite laminated photovoltaic device has significantly improved photoelectric conversion efficiency. This efficiency improvement enables the device to generate more electrical energy under the same lighting conditions, improving energy utilization efficiency. Through the improvement of interface passivation and the stability of perovskite materials, the product device provided by the embodiment of the present application shows excellent stability under environmental conditions such as humidity, temperature and light. This extends the service life of the device, reduces maintenance costs, and improves its reliability in practical applications. Its product device structure is simple and easy to integrate with other photovoltaic components or systems; this easy integration makes the device have broad application prospects in photovoltaic power stations, distributed energy systems and other fields. As a clean energy technology, the silicon-based perovskite laminated photovoltaic device provided in the embodiment of the present application does not generate pollutants during use and is environmentally friendly; at the same time, due to its efficient photoelectric conversion capability and stability, the device helps to promote the development of renewable energy and promote the transformation and upgrading of energy structure.

[0071] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

Claims

1. A silicon-based perovskite laminated photovoltaic device, characterized in that: It includes an interconnected silicon cell structure and a perovskite cell structure; The silicon cell structure comprises a crystalline silicon substrate, one side of which is sequentially provided with a first amorphous silicon intrinsic film, a p-type amorphous silicon film, an ITO layer and a silver layer; the other side of the crystalline silicon substrate is sequentially provided with a second amorphous silicon intrinsic film, an n-type amorphous silicon film and an anode layer; The perovskite cell structure comprises a perovskite layer, one side of the perovskite layer is sequentially provided with a first interface modification layer and a hole transport layer; the other side of the perovskite layer is sequentially provided with a second interface modification layer, an electron transport layer, a buffer layer, a window layer, a cathode layer and an anti-reflection layer; The anode layer is connected to the hole transport layer.

2. The silicon-based perovskite tandem photovoltaic device according to claim 1, characterized in that: The first interface modification layer is made of self-assembled layer material SAM1.

3. The silicon-based perovskite tandem photovoltaic device according to claim 2, characterized in that: The self-assembly layer material SAM1 includes any one or more of the following materials: CPA-1: CPA-2: CPA-3: CPA-4: CPA-5: CPA-6:

4. The silicon-based perovskite tandem photovoltaic device according to claim 1, characterized in that: The second interface modification layer is made of self-assembled layer material SAM2.

5. The silicon-based perovskite tandem photovoltaic device according to claim 4, characterized in that: The self-assembled layer material SAM2 includes any one or more of the following materials: CPA-7: CPA-8: CPA-9: CPA-10: CPA-11: CPA-12:

6. The silicon-based perovskite tandem photovoltaic device according to claim 1, characterized in that: The hole transport layer is a nickel oxide layer.

7. The silicon-based perovskite tandem photovoltaic device according to claim 6, characterized in that: An electron blocking layer and / or an exciton blocking layer is also arranged on the nickel oxide layer.

8. The silicon-based perovskite tandem photovoltaic device according to claim 1, characterized in that: The electron transport layer is C 60 layer.

9. The silicon-based perovskite tandem photovoltaic device according to claim 8, characterized in that: The C 60 A hole blocking layer and / or an exciton blocking layer is also arranged on the layer.

10. A method for preparing a silicon-based perovskite tandem photovoltaic device according to any one of claims 1 to 9, characterized in that: It includes the following steps: S1: preparing a crystalline silicon substrate, performing a texture process on one side thereof, and then cleaning the crystalline silicon substrate; S2: depositing a first amorphous silicon intrinsic film and a p-type amorphous silicon film in sequence on the textured side of the crystalline silicon substrate by a plasma enhanced chemical vapor deposition process; and depositing a second amorphous silicon intrinsic film and an n-type amorphous silicon film in sequence on the other side of the crystalline silicon substrate; S3: preparing an anode layer on the n-type amorphous silicon film by shadow mask sputtering; preparing an ITO layer on the p-type amorphous silicon film by shadow mask sputtering, and then sputtering a silver layer on the ITO layer; S4: Annealing the entire material to obtain a silicon cell structure; S5: preparing a hole transport layer on the anode layer by solution spin coating, preparing a first interface modification layer on the hole transport layer, and then preparing a perovskite layer on the first interface modification layer by solution processing; S6: preparing a second interface modification layer on the perovskite layer, preparing an electron transport layer on the second interface modification layer by thermal evaporation, and preparing a buffer layer on the electron transport layer by atomic deposition technology; S7: preparing a window layer on the buffer layer by sputtering, preparing a cathode layer on the window layer by thermal evaporation, and then preparing an anti-reflection layer on the cathode layer to obtain a finished photovoltaic device.

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