Structure of perovskite optoelectronic devices, their fabrication methods, and perovskite solar cells

Abstract

This invention discloses a perovskite optoelectronic device structure, its fabrication method, and a perovskite solar cell. The perovskite optoelectronic device structure includes a hole transport layer, a perovskite photosensitive layer, and an electron transport layer stacked along a specified direction. The hole transport layer comprises NiO. x A photoconductive thin film that conducts electricity under light is also disposed between the hole transport layer and the perovskite photosensitive layer; the photoconductive thin film contains a photoconductive material, and the photoconductive material is compatible with Ni. 2+ Complexation. The perovskite optoelectronic device structure and its fabrication method provided by this invention are not only simple and convenient to process, highly operable, and low in process cost, but also effectively improve the NiO complexation. x The conductivity of NiO is improved, thereby increasing the conversion efficiency and preventing NiO from deteriorating. x An interfacial reaction occurs with the perovskite photosensitive layer, thereby improving stability and promoting the rapid industrialization of perovskite solar cells.

Description

Technical Field

[0001] This invention relates to the field of optoelectronic device technology, and in particular to a perovskite optoelectronic device structure, its fabrication method, and a perovskite solar cell. Background Technology

[0002] In recent years, the development of perovskite solar cell technology has been rapid, with the efficiency of laboratory-sized cells increasing from 3.8% to 25.7%. Perovskite solar cells, with their superior photovoltaic performance, are gaining increasing favor from researchers and companies. Currently, several companies are committed to mass-producing perovskite solar cells, aiming to expedite the commercial application of perovskite solar cells and modules.

[0003] Perovskite solar cells are mainly divided into upright and inverted structures. Inverted perovskite solar cells are considered the mainstream technology for industrialization due to their better stability. In inverted structures, the commonly used hole transport layer materials fall into two main categories: one is organic materials based on PTAA, and the other is materials based on NiO. x It is primarily an inorganic material. Due to the high cost of PTAA, an organic material, and the poor wettability of perovskite solutions on PTAA, its application as a hole transport layer material in the mass production of perovskite solar cells and modules is limited.

[0004] NiO x Although NiO is considered by many researchers in the industry to be an important hole transport layer material for achieving mass production of perovskites due to its good electrical conductivity and mobility, as well as its simple preparation method, further research has revealed that improving NiO... x Chinese Ni 3+ The content of [specific element] can effectively reduce O vacancies, increase Ni vacancies, and effectively improve NiO [performance / quality]. x The conductivity of the perovskite solar cells and modules is improved, thereby increasing their efficiency.

[0005] But due to Ni 3+ The site is both a proton base and a Lewis acid. During the contact process with the perovskite photosensitive layer, as a proton base, it causes the organic amine in the perovskite photosensitive layer to deprotonate. At the same time, as a Lewis acid, it oxidizes iodide ions. Ultimately, the NiOx and perovskite photosensitive layer interface undergoes a redox reaction, which leads to instability between the perovskite photosensitive layer and the perovskite interface. This is detrimental to the photovoltaic performance and long-term stability of perovskite solar cells and modules.

[0006] NiO x Chinese Ni 3+ The characteristics of perovskite lead to contradictory problems in the preparation of efficient and stable perovskite solar cells and modules.

[0007] For example, one type of existing technology is to use NiO x Sintering or NiO x Ultraviolet ozone treatment effectively improves NiO x Chinese Ni 3+ The content of NiO was thus increased, thereby increasing the content of NiO. x The conductivity of N increases the efficiency of corresponding batteries and components, but due to N 3+ The problem of redox reactions with the perovskite photosensitive layer remains unresolved, thus sacrificing the stability of the corresponding perovskite solar cells and modules.

[0008] Another type of existing technology is based on NiO. x The surface is coated with a non-conductive organic polymer layer. Although the insertion of this non-conductive organic polymer layer can effectively improve the stability of perovskite solar cells and modules, its non-conductive nature limits its thickness and increases the series resistance of the entire perovskite solar cell and module. As a result, the efficiency of perovskite solar cells and modules prepared by this technology is limited, sacrificing the efficiency of the corresponding perovskite solar cells and modules.

[0009] Therefore, the existing solutions do not fundamentally solve the NiO problem. x Due to Ni 3+ The inherent contradictions in the properties of NiO. To expedite the industrialization of perovskite solar cells, it is necessary to address the issue of improving NiO properties. x The conductivity and prevention of NiO x An effective solution is proposed to address the two contradictory problems of interfacial reactions with perovskites. Summary of the Invention

[0010] To address the shortcomings of existing technologies, the present invention aims to provide a perovskite optoelectronic device structure, its fabrication method, and a perovskite solar cell, specifically targeting the improvement of NiO... x The conductivity and prevention of NiO x An effective solution is proposed to address the two contradictory problems of interfacial reactions with perovskites.

[0011] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0012] In a first aspect, the present invention provides a perovskite optoelectronic device structure, comprising a hole transport layer, a perovskite photosensitive layer, and an electron transport layer stacked along a specified direction, wherein the hole transport layer comprises NiO. x A photoconductive thin film that conducts electricity under light is further disposed between the hole transport layer and the perovskite photosensitive layer; the photoconductive thin film contains a photoconductive material, and the photoconductive material is capable of reacting with Ni. 2+Complexed with and associated with a portion of Ni in the hole transport layer 2+ Complexation.

[0013] In a second aspect, the present invention also provides a method for fabricating a perovskite optoelectronic device structure, comprising the steps of fabricating a hole transport layer, a perovskite photosensitive layer, and an electron transport layer, wherein the perovskite photosensitive layer is disposed between the hole transport layer and the electron transport layer, and the fabrication method further comprises:

[0014] A photoconductive thin film is disposed between the hole transport layer and the perovskite photosensitive layer. The photoconductive thin film contains a photoconductive material that is capable of reacting with Ni. 2+ The complexed hole transport layer comprises NiO x .

[0015] Thirdly, the present invention also provides a perovskite solar cell, comprising the above-mentioned perovskite optoelectronic device structure and a first electrode and a second electrode; the first electrode is electrically connected to the hole transport layer of the perovskite optoelectronic device structure, and the second electrode is electrically connected to the electron transport layer of the perovskite optoelectronic device structure, thereby constituting a complete perovskite solar cell.

[0016] Fourthly, the present invention also provides a solar cell module composed of the above-mentioned perovskite solar cells, which may be composed of at least a plurality of the perovskite solar cells electrically connected together.

[0017] In the above technical solution, the perovskite optoelectronic device structure and its fabrication method provided by the present invention utilize NiO x A photoconductive thin film containing a photoconductive material is inserted between the hole transport layer and the perovskite photosensitive layer. This photoconductive material not only conducts electricity under illumination, reducing resistance during illumination, but also interacts with NiO. x Ni on the surface 2+ Complexation, thereby transferring charge to NiO x This increases NiO x This increases the hole concentration and conductivity, improving the efficiency of corresponding perovskite solar cells and modules; simultaneously, because photoconductive thin films can not only deepen the hole concentration and conductivity of NiO, but also improve the efficiency of perovskite solar cells and modules. x The valence band and Fermi level of NiO enable NiO to... x The energy levels of NiOx are better matched to those of perovskite, suppressing energy loss between the hole transport layer and the perovskite photosensitive layer, thus increasing the voltage of the corresponding perovskite solar cells and modules. Furthermore, under the condition of light-induced conductivity, it can prevent direct contact between NiOx and the perovskite photosensitive layer, thereby preventing NiO from... x Ni in 3+ It undergoes a redox reaction with perovskite, thereby improving the efficiency and stability of the corresponding perovskite solar cells and modules.

[0018] Based on the above technical solution and its principles, compared with the prior art, the beneficial effects of the present invention include at least the following:

[0019] The preparation method provided by this invention is not only simple and convenient, highly operable, and low in cost, but also effectively improves the NiO content. x The conductivity of NiO is improved, thereby enhancing the conductivity of NiO. x The conversion efficiency of perovskite solar cells and modules fabricated with hole transport layers is improved, while also preventing NiO from being affected. x The interfacial reaction with the perovskite photosensitive layer improves the stability of the corresponding perovskite solar cells and modules, thus promoting the rapid industrialization of perovskite solar cells.

[0020] The above description is merely an overview of the technical solution of the present invention. In order to enable those skilled in the art to better understand the technical means of this application and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described below in conjunction with detailed drawings. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell provided in an embodiment of the present invention.

[0022] Explanation of reference numerals in the attached figures: 100, perovskite solar cell; 110, perovskite optoelectronic device structure; 120, first electrode; 130, second electrode; 140, carrier glass;

[0023] 111. Perovskite photosensitive layer; 112. Hole transport layer; 113. Electron transport layer; 114. Photoconductive thin film. Detailed Implementation

[0024] The inventors of this invention have discovered through long-term practical research that the existing technology using NiO... x Perovskite solar cells, which serve as hole transport layers, have the following problems:

[0025] 1. NiO x Ni in 3+ Increasing the content of NiO is beneficial to improving NiO content. x The conductivity of Ni, but due to Ni 3+ The site is both a proton base and a Lewis acid, which can not only deprotonate organic amines in the perovskite photosensitive layer, but also oxidize iodide ions, thereby causing a redox reaction with the perovskite photosensitive layer and making the corresponding perovskite solar cells and modules unstable. NiO x Due to Ni 3+ The properties of this lead to a contradiction between conductivity and stability.

[0026] 2. NiO xHigh-temperature sintering or ultraviolet ozone treatment can significantly improve the performance of NiO. x Chinese Ni 3+ The content of NiO is thus increased. x The conductivity of Ni, but due to Ni 3+ Increased content will lead to NiO x The redox reaction with the perovskite photosensitive layer leads to instability in the corresponding perovskite solar cells and modules.

[0027] 3. Some existing technologies in NiO x The coating of non-conductive polymer material can prevent NiO from being exposed to the elements. x A redox reaction occurs between the perovskite photosensitive layer and the material, improving the stability of the corresponding perovskite solar cells and modules. However, because the material is non-conductive, this increases the series resistance of the cells and modules. This approach makes using NiO... x The efficiency of perovskite solar cells and modules fabricated with hole transport layers is limited.

[0028] In view of the shortcomings of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. The following will further explain and illustrate the technical solution, its implementation process, and its principles.

[0029] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and therefore the scope of protection of the invention is not limited to the specific embodiments disclosed below.

[0030] Moreover, relational terms such as “first” and “second” are used merely to distinguish one component or method step from another that has the same name, without necessarily requiring or implying any such actual relationship or order between these components or method steps.

[0031] See Figure 1 This invention provides a perovskite optoelectronic device structure 110, comprising a hole transport layer 112, a perovskite photosensitive layer 111, and an electron transport layer 113 stacked along a specified direction. The hole transport layer 112 comprises NiO. x A photoconductive thin film 114, which conducts electricity under light, is further disposed between the hole transport layer 112 and the perovskite photosensitive layer 111; the photoconductive thin film 114 comprises a photoconductive material, and the photoconductive material is bonded to a portion of the Ni in the hole transport layer 112. 2+ Complexation.

[0032] The key point of the above technical solution is that the photoconductive material used has both photoconductivity and complexing and barrier properties, forming a multifunctional photoconductive thin film 114.

[0033] In some embodiments, the thickness of the photoconductive thin film 114 can be 5-20 nm.

[0034] In some embodiments, the hole transport layer 112 may have a thickness of 20-100 nm, and the electron transport layer 113 may have a thickness of 40-100 nm.

[0035] This invention also provides a method for fabricating the above-mentioned perovskite optoelectronic device structure 110, including the steps of fabricating a hole transport layer, a perovskite photosensitive layer, and an electron transport layer, wherein the perovskite photosensitive layer is disposed between the hole transport layer and the electron transport layer; the fabrication method further includes:

[0036] A photoconductive thin film is disposed between the hole transport layer and the perovskite photosensitive layer. The photoconductive thin film contains a photoconductive material that is capable of reacting with Ni. 2+ The complex, wherein the hole transport layer comprises nickel oxide.

[0037] In some preferred embodiments, the following steps are specifically included:

[0038] 1) Forming a hole transport layer 112, the hole transport layer 112 comprising NiO x .

[0039] 2) A precursor for a photoconductive thin film 114, comprising a photoconductive material, is formed on the surface of the hole transport layer 112, and the hole transport layer 112 and the precursor for the photoconductive thin film 114 are subjected to heat treatment to form a photoconductive thin film 114 on the surface of the hole transport layer 112, wherein the photoconductive material is capable of reacting with Ni. 2+ Complexation.

[0040] 3) A perovskite photosensitive layer 111 is formed on the surface of the photoconductive thin film 114.

[0041] 4) An electron transport layer 113 is formed on the surface of the perovskite photosensitive layer 111.

[0042] One step may be: coating a precursor solution of a photoconductive material onto a hole transport layer and then heating it to form a photoconductive thin film. Another step may be: coating a perovskite precursor solution onto the photoconductive thin film and then annealing it to form the perovskite photosensitive layer.

[0043] In some implementations, step 1) may specifically include:

[0044] A precursor solution comprising the photoconductive material is provided.

[0045] The precursor solution is coated onto the surface of the hole transport layer 112 to form the precursor of the photoconductive thin film 114.

[0046] In some embodiments, the photoconductive material may include any one or a combination of two or more of phthalocyanine, phthalocyanine derivatives, porphyrin, and porphyrin derivatives. While there are existing technologies that utilize porphyrin and porphyrin derivatives for interface modification of the hole transport layer, their principles differ from those of this invention. These technologies primarily utilize the morphology modification and barrier properties of porphyrin and porphyrin derivatives, rather than incorporating NiO as described in this invention. x It interacts with photoconductive materials to achieve multiple functional effects. An example hole transport layer is PEODT:PSS, which is currently considered unsuitable for commercial applications due to its poor hole transport performance.

[0047] In some embodiments, the concentration of the photoconductive material in the precursor solution can be 2-10 mg / ml.

[0048] In some embodiments, the heat treatment temperature can be 80-120°C and the time can be 5-15 minutes.

[0049] In some embodiments, the coating method of the precursor solution may include any one or a combination of two or more of spin coating, coating and spraying.

[0050] In some embodiments, the hole transport layer 112 may be prepared by any one or a combination of two or more of the following methods: vacuum deposition, solution method, and sol-gel method.

[0051] This invention also provides a perovskite solar cell, including the perovskite optoelectronic device structure 110 provided or fabricated above, a first electrode 120, and a second electrode 130; the first electrode 120 is electrically connected to the hole transport layer 112 of the perovskite optoelectronic device structure 110, and the second electrode 130 is electrically connected to the electron transport layer 113 of the perovskite optoelectronic device structure 110.

[0052] Based on the above overview of the technical solutions, as an example and as some specific implementation cases, the present invention also provides a perovskite solar cell, including a carrier glass 140, a transparent conductive thin film electrode disposed on the carrier glass 140 as a first electrode 120, a top-layer metal electrode as a second electrode 130, and a perovskite optoelectronic device structure 110 located between the transparent conductive thin film electrode and the metal electrode.

[0053] The perovskite optoelectronic device structure 110 may include a perovskite photosensitive layer 111 and a hole transport layer 112 located on one side of the perovskite photosensitive layer 111, which includes NiO. x A photoconductive thin film 114 of phthalocyanine / porphyrin and its derivatives is inserted between the hole transport layer 112 and the perovskite photosensitive layer 111, and an electron transport layer 113 is located on the other side of the perovskite photosensitive layer 111.

[0054] The perovskite solar cell, in NiO x Inserting a photoconductive thin film 114 of phthalocyanine / porphyrin and its derivatives between the hole transport layer 112 and the perovskite photosensitive layer 111 not only effectively improves the conductivity of NiOx, but also effectively prevents the instability of the NiOx / perovskite photosensitive layer 111 interface caused by redox reaction between NiOx and the perovskite photosensitive layer 111, thereby improving the stability of the corresponding perovskite solar cells and modules. In addition, the method has a simple preparation process, strong operability, and low process cost, which is conducive to rapidly promoting the industrialization of perovskite solar cells.

[0055] The primary function of the carrier glass 140 is to serve as a carrier for the transparent conductive thin-film electrode. The carrier glass 140 can be any base glass used in conductive glass applications. Preferably, the thickness of the carrier glass 140 is 1.1 mm to 2.5 mm. This ensures sufficient mechanical load-bearing capacity while reducing light absorption by the carrier glass 140, allowing more light to enter the battery's main structure and thus increasing the battery's light absorption and utilization rate.

[0056] The main function of both transparent conductive thin film electrodes and metal electrodes is to conduct photocurrent.

[0057] In this embodiment, the transparent conductive film electrode is an FTO electrode, also known as a fluorine-doped tin oxide electrode. This enhances the absorption of ultraviolet light by the transparent conductive film electrode, further reducing the amount of ultraviolet light entering the electron transport layer 113. Furthermore, the FTO electrode also has the advantages of low resistivity and stable chemical properties. Of course, it is understood that the transparent conductive film electrode is not limited to an FTO electrode; it can also be an indium tin oxide (ITO), indium titanium oxide (ITiO), indium cerium oxide (ICO), indium tungsten oxide (IWO), zinc aluminum oxide (AZO), or zinc boron oxide (BZO).

[0058] In this embodiment, the metal electrode is preferably a silver (Ag) electrode. Of course, it is understood that the metal electrode 130 is not limited to a silver (Ag) electrode, but can also be an electrode made of other metals, such as a gold (Au) electrode or an aluminum (Al) electrode.

[0059] NiOx The main function of the hole transport layer 112 is to transport holes, while also blocking electrons. Preferably, the thickness of the hole transport layer 112 is 20–100 nm. This ensures film quality, reduces defects in the hole transport layer 112, and also ensures low internal series resistance, which is beneficial for increasing short-circuit current. In this embodiment, NiO... x The hole transport layer 112 is directly vacuum deposited on the transparent conductive thin film bottom electrode (FTO).

[0060] Insertion of NiO x The main function of the photoconductive thin film 114 between the hole transport layer 112 and the perovskite photosensitive layer 111 is to transfer charge from the photoconductive thin film to NiO under illumination, as the photoconductive material conducts electricity. x Above, improve NiO x The conductivity and hole concentration of NiO were improved. x Conductivity, and improve the overall conductivity of the battery under light, deepening the NiO layer. x The valence band and Fermi level of NiO enable NiO to... x The energy levels of NiO are more closely matched with those of perovskite, reducing the need for NiO. x Energy loss at the perovskite interface is reduced, thereby improving the efficiency of the corresponding perovskite solar cells and modules. Furthermore, the photoconductive thin film 114 effectively isolates NiO. x Direct contact with the perovskite photosensitive layer 111 effectively prevents NiO. x It undergoes a redox reaction with the perovskite photosensitive layer 111, increasing the efficiency of NiO. x The stability of the interface with the perovskite photosensitive layer 111 is improved, thereby enhancing the stability of the perovskite solar cell and module.

[0061] The main function of the electron transport layer 113 is to transport electrons while also blocking holes, thereby reducing electron-hole recombination and selectively transporting electrons. Preferably, the thickness of the electron transport layer 113 is 40–100 nm. This ensures film quality, reduces defects during electron transport, and maintains low internal series resistance, which is beneficial for increasing short-circuit current. In this embodiment, the electron transport layer 113 is preferably a PCBM, which can be directly coated on the perovskite photosensitive layer 111.

[0062] In one embodiment, the photoconductive thin film 114 is made of NiO. x Between the hole transport layer 112 and the perovskite photosensitive layer 111.

[0063] In one embodiment, the photoconductive thin film 114 is prepared by coating a NiO film with a precursor solution consisting of photoconductive materials phthalocyanine / porphyrin and their derivatives dissolved in DMF. x The above is heated at 80℃~120℃ for 5~15min to form a film. Under this solvent, phthalocyanine / porphyrin and its derivative photoconductive materials can be well dissolved. Of course, other solvents that can fully dissolve photoconductive materials and can be formed into films by heating annealing or anti-solvent methods are also acceptable.

[0064] In one embodiment, the concentration of the photoconductive material solution is 2 mg / mL to 10 mg / mL. The photoconductive layer prepared at this concentration can effectively prevent NiO from... x Contact with the perovskite photosensitive layer 111 enhances the NiO x This improves the stability of the perovskite interface and maximizes the transfer of charge from the photoconductive layer to NiO. x Hole transport layer 112, NiO x The hole concentration and conductivity are optimized, thereby maximizing the efficiency of the corresponding perovskite solar cells and modules.

[0065] In the above implementation examples, in NiO x A thin film of photoconductive phthalocyanine / porphyrin and its derivatives is inserted between the hole transport layer 112 and the perovskite photosensitive layer 111. This is because the photoconductive phthalocyanine / porphyrin and its derivatives not only conduct electricity under illumination but also react with NiO. x Ni on the surface 2+ Complexation, thereby transferring charge to NiO x This increases NiO x This improves the hole concentration and conductivity, thereby increasing the efficiency of corresponding perovskite solar cells and modules. Simultaneously, due to the coating of NiO with phthalocyanine / porphyrin and its derivatives... x On top, it can not only deepen NiO x The valence band and Fermi level of NiO enable NiO to... x Its energy levels are better matched to perovskite, suppressing perovskite NiO x Energy loss at the interface is reduced, increasing the voltage of corresponding perovskite solar cells and modules. Furthermore, due to the insertion of photoconductive thin films of perovskite solar cells and their derivatives into NiO, [the energy loss is reduced]. x Between the perovskite photosensitive layer 111 and NiO, it can prevent NiO x Direct contact with the perovskite photosensitive layer 111, thereby preventing NiO x Ni in 3+A redox reaction occurs with perovskite, thereby improving the efficiency and stability of the corresponding perovskite solar cells and modules. The method provided in this invention is not only simple and convenient, highly operable, and low in cost, but also effectively improves the efficiency of NiO. x The conductivity of NiOx is improved, thereby increasing the efficiency of perovskite solar cells and modules fabricated with NiOx as the hole transport layer 112, while also preventing NiO from deteriorating. x An interfacial reaction occurs with the perovskite photosensitive layer 111, thereby improving the stability of the corresponding perovskite solar cells and modules, and promoting the rapid development of the perovskite solar cell industry.

[0066] This invention also provides a solar module, which can be constructed by electrically connecting multiple perovskite solar cells as described above. Of course, it is understood that in addition to perovskite solar cells, the perovskite solar module also includes other components, such as structural components, protective components, and rectifier and transformer devices, etc. The selection of these components and their specific structures can be set by those skilled in the art according to the actual situation, and will not be elaborated here.

[0067] The perovskite solar module described above, by employing the perovskite solar cell provided by this invention, improves the efficiency and stability of the perovskite solar cell, thereby improving the efficiency and stability of the perovskite solar module, while reducing the process cost of preparing a high-efficiency and stable perovskite solar module.

[0068] To enable those skilled in the art to fully understand the present invention, the technical solutions of the present invention are further described in detail below through several more specific embodiments and in conjunction with the accompanying drawings. However, the selected embodiments are only for illustrating the present invention and do not limit the scope of the present invention.

[0069] Example 1

[0070] This embodiment illustrates the fabrication process of a perovskite solar cell, as detailed below:

[0071] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0072] A phthalocyanine solution with a concentration of 6 mg / mL DMF was spin-coated onto the hole transport layer 112 at a rotation speed of 2500 r / s, and then heated at 100 °C for 10 min to form a photoconductive thin film 114 with a thickness of ~13 nm.

[0073] A ternary component FA with a concentration of 1.2 M was spin-coated onto a photoconductive thin film 114. 0.85 MA 0.10 Cs 0.05A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0074] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0075] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain a perovskite solar cell A1.

[0076] Example 2

[0077] This embodiment illustrates the fabrication process of a perovskite solar cell, as detailed below:

[0078] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0079] A phthalocyanine solution dissolved in DMF of 2 mg / mL was spin-coated onto the hole transport layer 112 at a rotation speed of 2500 r / s, and then heated at 80 °C for 5 min to form a photoconductive thin film 114 with a thickness of ~5 nm.

[0080] A ternary component FA with a concentration of 1.2 M was spin-coated onto a photoconductive thin film 114. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0081] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0082] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain the perovskite solar cell A2.

[0083] Example 3

[0084] This embodiment illustrates the fabrication process of a perovskite solar cell, as detailed below:

[0085] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0086] A phthalocyanine solution dissolved in DMF of 10 mg / mL was spin-coated onto the hole transport layer 112 at a rotation speed of 2500 r / s, and then heated at 120 °C for 15 min to form a photoconductive thin film 114 with a thickness of ~20 nm.

[0087] Spin-coating a ternary component FA at a concentration of 114 onto a photoconductive thin film 114 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0088] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0089] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain a perovskite solar cell A3.

[0090] Example 4

[0091] This embodiment illustrates the fabrication process of a perovskite solar cell, as detailed below:

[0092] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0093] A photoconductive thin film 114 with a thickness of ~13 nm was formed by spin-coating a porphyrin solution dissolved in DMF at a rotation speed of 2500 r / s onto the hole transport layer 112 and heating it at 100 °C for 10 min.

[0094] A ternary component FA with a concentration of 1.2 M was spin-coated onto a photoconductive thin film 114. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0095] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0096] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain a perovskite solar cell A4.

[0097] Example 5

[0098] This embodiment illustrates the fabrication process of a perovskite solar cell, as detailed below:

[0099] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0100] A phthalocyanine solution dissolved in DMF at a concentration of 6 mg / mL was sprayed onto the hole transport layer 112. The spraying flow rate was 0.2 mL / min, the spraying time was 20 s, and the spraying pressure was 0.2 MPa. After spraying, the film was heated at 100 °C for 10 min to form a photoconductive thin film 114 with a thickness of ~13 nm.

[0101] A ternary component FA with a concentration of 1.2 M was spin-coated onto a photoconductive thin film 114. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0102] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0103] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain a perovskite solar cell A5.

[0104] Example 6

[0105] This embodiment illustrates the fabrication process of a perovskite solar cell, as detailed below:

[0106] A FTO transparent electrode was deposited on a clean, transparent substrate glass. Then, an ethylene glycol solution containing 1M nickel nitrate hexahydrate and ethylenediamine was spin-coated onto the FTO transparent electrode at a speed of 3000 r / s. Subsequently, the electrode was heated at 400 °C for 30 min to form a 40 nm NiO layer. x Thus, hole transport layer 112 is obtained.

[0107] A photoconductive thin film 114 with a thickness of ~13 nm is formed by spin-coating a phthalocyanine solution with a concentration of 6 mg / mL of DMF onto the hole transport layer 112 at a rotation speed of 2500 r / s and heating it at 100 °C for 10 min.

[0108] A ternary component FA with a concentration of 1.2 M was spin-coated onto a photoconductive thin film 114. 0.85 MA 0.10 Cs 0.05A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0109] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0110] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain a perovskite solar cell A6.

[0111] Example 7

[0112] This embodiment is largely the same as Embodiment 1, with the only difference being:

[0113] The ternary component FA in Example 1 0.85 MA 0.10 Cs 0.05 PbI3 perovskite solution replaced with binary component FA 0.85 Cs 0.15 PbI3 perovskite solution, with other conditions unchanged.

[0114] The obtained perovskite solar cell was tested and found to have similar performance characteristics to that of Example 1.

[0115] Example 8

[0116] This embodiment is largely the same as Embodiment 1, with the only difference being:

[0117] The ternary component FA in Example 1 0.85 MA 0.10 Cs 0.05 Replace the PbI3 perovskite solution with FAPbI3 perovskite solution, keeping all other conditions unchanged.

[0118] The obtained perovskite solar cell was tested and found to have similar performance characteristics to that of Example 1.

[0119] Example 9

[0120] This embodiment is largely the same as Embodiment 1, with the only difference being:

[0121] The ternary component FA in Example 1 0.85 MA 0.10 Cs 0.05 The PbI3 perovskite solution was replaced with MAPbI3 perovskite solution, and the perovskite photosensitive layer 111 was formed by annealing at 100℃ for 15 min, while other conditions remained unchanged.

[0122] The obtained perovskite solar cell was tested and found to have similar performance characteristics to that of Example 1.

[0123] Example 10

[0124] This embodiment is largely the same as Embodiment 1, with the only difference being:

[0125] Replace the phthalocyanine solution in Example 1 with a naphthocyanin solution, keeping all other conditions unchanged.

[0126] The obtained perovskite solar cell was tested and found to have similar performance characteristics to that of Example 1.

[0127] Example 11

[0128] After aging the perovskite solar cell A1 in air for 400 hours, its photovoltaic performance was tested, and it was found that the efficiency of the perovskite solar cell A1 after aging was 96% of that before aging.

[0129] Comparative Example 1

[0130] The fabrication process of this comparative example, a perovskite solar cell, is shown below:

[0131] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0132] A ternary component FA at a concentration of 1.2 M was spin-coated onto the hole transport layer 112. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0133] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0134] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain the perovskite solar cell B1.

[0135] Comparative Example 2

[0136] The fabrication process of this comparative example, a perovskite solar cell, is shown below:

[0137] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0138] A phthalocyanine solution with a concentration of 1 mg / mL DMF was spin-coated onto the hole transport layer 112 at a rotation speed of 2500 r / s, and then heated at 100 °C for 10 min to form a photoconductive thin film 114 with a thickness of ~2 nm.

[0139] A ternary component FA with a concentration of 1.2 M was spin-coated onto a photoconductive thin film 114. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0140] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0141] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain the perovskite solar cell B2.

[0142] Comparative Example 3

[0143] The fabrication process of this comparative example, a perovskite solar cell, is shown below:

[0144] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0145] A phthalocyanine solution with a concentration of 12 mg / mL DMF was spin-coated onto the hole transport layer 112 at a rotation speed of 2500 r / s, and then heated at 100 °C for 10 min to form a photoconductive thin film 114 with a thickness of ~25 nm.

[0146] A ternary component FA with a concentration of 1.2 M was spin-coated onto a photoconductive thin film 114. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0147] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0148] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain the perovskite solar cell B3.

[0149] Comparative Example 4

[0150] The fabrication process of this comparative example, a perovskite solar cell, is shown below:

[0151] FTO transparent electrodes were deposited on a clean, transparent substrate glass by vapor deposition, and then 40 nm of NiO was deposited on the FTO transparent electrodes by magnetron sputtering vacuum deposition. x Thus, hole transport layer 112 is obtained.

[0152] A porphyrin solution dissolved in DMF with a concentration of 6 mg / mL was spin-coated onto the hole transport layer 112 at a rotation speed of 2500 r / s, and then dried overnight at room temperature to form a modified layer.

[0153] A ternary component FA at a concentration of 1.2 M was spin-coated onto the modified layer. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0154] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0155] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain the perovskite solar cell B4.

[0156] Comparative Example 5

[0157] The fabrication process of this comparative example, a perovskite solar cell, is shown below:

[0158] A FTO transparent electrode was deposited on a clean, transparent substrate glass. Then, an ethylene glycol solution containing 1M nickel nitrate hexahydrate and ethylenediamine was spin-coated onto the FTO transparent electrode at a speed of 3000 r / s. Subsequently, the electrode was heated at 400 °C for 30 min to form a 40 nm NiO layer. x Thus, hole transport layer 112 is obtained.

[0159] A ternary component FA at a concentration of 1.2 M was spin-coated onto the hole transport layer 112. 0.85 MA 0.10 Cs 0.05 A PbI3 perovskite solution was annealed at 130°C for 15 min to form a perovskite photosensitive layer 111.

[0160] A chlorobenzene solution of PCBM (PCBM concentration of 20 mg / mL) was spin-coated onto the perovskite photosensitive layer 111 at a speed of 3000 r / s and annealed at 100 °C for 10 min to form an electron transport layer 113.

[0161] Finally, a metal electrode Ag was vapor-deposited on the electron transport layer 113 to obtain the perovskite solar cell B5.

[0162] Comparative Example 6

[0163] After aging the perovskite solar cell B1 in air for 400 hours, its photovoltaic performance was tested, and it was found that the efficiency of the perovskite solar cell B1 after aging was only 48% of that before aging.

[0164] The perovskite solar cells A1-A6 and B1-B5 obtained in Examples 1-6 and Comparative Examples 1-5 were tested using a simulated light source system, and the relevant performance test results are shown in Table 1.

[0165] Table 1. Photovoltaic performance test results of perovskite solar cells A1-A6 and B1-B5 obtained in Examples 1-6 and Comparative Examples 1-5.

[0166]

[0167]

[0168] As can be seen from Table 1, the present invention is used in NiO x The perovskite solar cells A1-A5 prepared by inserting a photoconductive thin film 114 made of a photoconductive material between the hole transport layer 112 and the perovskite photosensitive layer 111 exhibit significantly higher open-circuit voltage (Voc), short-circuit current (Jsc), and fill factor (FF) than the perovskite solar cell B1 prepared without the method provided in this invention. This is mainly because, in this invention, a photoconductive thin film made of a photoconductive material is inserted between NiOx and the perovskite photosensitive layer 111. Under illumination, the photoconductive material can conduct electricity and interacts with NiOx. x Ni on the surface 2+ Complexation effectively transfers charge from the photoconductive thin film to NiO. x This effectively improves NiO x The hole concentration and conductivity of NiO are increased. x The electrical conductivity, and the photoconductive material can also conduct NiO. x The valence band and Fermi level are deepened, making them more compatible with the 111 energy level of the perovskite photosensitive layer, thus reducing the energy loss of NiO. xThe energy loss between the perovskite photosensitive layer 111 and the perovskite photosensitive layer 111 is reduced, thereby improving the open-circuit voltage (Voc), short-circuit current (Jsc), and fill factor (FF) of the fabricated perovskite solar cell, resulting in a significant increase in the efficiency of the final perovskite solar cell. Comparing Examples 1-3 and Comparative Example 4, it was found that the perovskite solar cells A1-A3 fabricated using the photoconductive thin film 114 made of photoconductive material on NiOx according to the present invention have much better photovoltaic performance than the perovskite solar cell B4 fabricated by only forming a modification layer without heating the photoconductive material to form a photoconductive thin film. This is mainly because the present invention inserts a photoconductive material between NiOx and the perovskite photosensitive layer 111 through a heating process to form a photoconductive thin film. Under illumination, the photoconductive material can conduct electricity and interacts with NiOx. x Ni on the surface 2+ Complexation effectively transfers charge from the photoconductive thin film to NiO. x This effectively improves NiO x The hole concentration and conductivity of NiO are increased. x The conductivity further improves the photovoltaic performance of perovskite solar cells.

[0169] Meanwhile, by comparing Examples 1-3 and Comparative Examples 2-3, it was found that the perovskite solar cells A1-A3 prepared using the photoconductive thin film 114 composed of the photoconductive material within the concentration range of the present invention have higher efficiency than the perovskite solar cells B2-B3 prepared without the photoconductive thin film 114 composed of the photoconductive material within the concentration range of the present invention. This is mainly because the photoconductive material within the concentration range of the present invention forms a more complete complex with NiOx and maximizes the transfer of charge from the photoconductive layer to NiO. x Hole transport layer.

[0170] Meanwhile, by comparing Example 6 and Comparative Example 5, it was found that the photovoltaic performance of the perovskite solar cell A6, which uses a photoconductive thin film made of photoconductive material on NiOx prepared by solution method, is much better than that of the perovskite solar cell B5, which is prepared without the photoconductive material of the present invention. This further demonstrates that the photoconductive material of the present invention is not only applicable to vacuum-deposited NiOx as a hole transport layer, but also to NiOx structures prepared by solution method or sol-gel method as a hole transport layer.

[0171] Furthermore, by comparing Example 11 and Comparative Example 6, we found that the perovskite solar cell A1 prepared using the photoconductive thin film made of photoconductive material on NiOx according to the present invention showed significantly lower efficiency degradation and significantly improved stability compared to the perovskite solar cell B1 prepared without the present invention, after 400 hours of light aging under the same environment (air environment). This is mainly because the insertion of the photoconductive material thin film effectively prevents NiO from being absorbed by the film. x It is in direct contact with the perovskite photosensitive layer 111, thereby effectively preventing NiO from... x An interfacial reaction occurs with the perovskite photosensitive layer 111, enhancing the performance of NiO. x The interface stability with the perovskite photosensitive layer 111 is improved, thereby enhancing the stability of the corresponding perovskite solar cells and modules.

[0172] Based on the above embodiments and comparative examples, it can be clearly understood that:

[0173] 1. This invention relates to NiO x A photoconductive thin film 114 made of a photoconductive material is inserted between the perovskite interface and the perovskite. Because the photoconductive material can conduct electricity under light conditions and can interact with NiO... x Ni in the upper surface 2+ Complexation effectively transfers charge from the photoconductive material to NiO. x Above, improved NiO x The hole concentration and conductivity of NiO were improved. x The conductivity of the perovskite solar cells and modules is improved, thereby increasing their efficiency.

[0174] 2. This invention relates to NiO x Inserting a photoconductive thin film 114 between the NiO and the perovskite interface can effectively deepen the NiO layer. x The valence band and Fermi level, thus enabling NiO x The energy levels of NiO are more closely matched with those of the perovskite photosensitive layer 111, thereby reducing the energy loss of NiO. x Energy loss at the perovskite photosensitive layer 111 interface, thereby increasing the voltage of the corresponding perovskite solar cells and modules.

[0175] 3. This invention relates to NiO x Inserting a photoconductive thin film 114 between the perovskite and the perovskite interface can effectively prevent the perovskite photosensitive layer 111 from reacting with NiO. x Direct contact effectively prevents NiO x Ni in 3+ It undergoes a redox reaction with the perovskite photosensitive layer 111, thereby enhancing the NiO content. x The stability of the perovskite photosensitive layer 111 interface is improved, thereby enhancing the stability of the corresponding perovskite solar cells and modules.

[0176] 4. The preparation method provided by this invention substantially solves the problem of using NiO x As a hole transport layer 112, perovskite solar cells and modules are fabricated due to the presence of Ni. 3+ This invention addresses the inherent contradiction between high efficiency and stability arising from the characteristics of perovskite solar cells. Furthermore, the fabrication method provided by this invention is simple, convenient, easy to operate, and low in cost, thus facilitating the rapid industrialization of perovskite solar cells.

[0177] It should be understood that the above embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A perovskite optoelectronic device structure, comprising a hole transport layer, a perovskite photosensitive layer, and an electron transport layer stacked along a specified direction, wherein the hole transport layer comprises NiO. x Its characteristics are, A photoconductive thin film is also disposed between the hole transport layer and the perovskite photosensitive layer. The photoconductive thin film prevents the hole transport layer NiO x Ni in 3+ It undergoes a redox reaction with the perovskite photosensitive layer; Furthermore, the photoconductive thin film comprises a photoconductive material, and the photoconductive material is connected to the hole transport layer NiO. x Part of Ni 2+ Complexation; The photoconductive material includes any one or more combinations of phthalocyanine or phthalocyanine derivatives, porphyrin or porphyrin derivatives.

2. The perovskite optoelectronic device structure according to claim 1, characterized in that, The thickness of the photoconductive thin film is 5-20 nm; And / or, the photoconductive thin film is directly coated on the surface of the hole transport layer.

3. A method for fabricating a perovskite optoelectronic device structure, comprising the steps of fabricating a hole transport layer, a perovskite photosensitive layer, and an electron transport layer, wherein the hole transport layer comprises NiO. x The perovskite photosensitive layer is disposed between the hole transport layer and the electron transport layer; characterized in that, The preparation method further includes: A photoconductive thin film is disposed between the hole transport layer and the perovskite photosensitive layer to prevent the hole transport layer NiO x Ni in 3+ The perovskite photosensitive layer undergoes a redox reaction, and the photoconductive thin film contains a photoconductive material that can react with the hole transport layer NiO. x Ni in 2+ Complexation.

4. The preparation method according to claim 3, characterized in that, Specifically, it includes: A precursor solution of a photoconductive material is coated onto a hole transport layer and then heated to form a photoconductive thin film.

5. The preparation method according to claim 4, characterized in that, Also includes: The perovskite precursor solution is coated onto a photoconductive thin film and then annealed to form the perovskite photosensitive layer.

6. The preparation method according to claim 4, characterized in that, The concentration of the photoconductive material in the precursor solution is 2-10 mg / ml.

7. The preparation method according to claim 4, characterized in that, The heat treatment is performed at a temperature of 80-120℃ for 5-15 minutes.

8. The preparation method according to claim 4, characterized in that, The coating method for the precursor solution includes any one or a combination of two or more of spin coating, coating, and spraying.

9. The preparation method according to claim 4, characterized in that, The method for preparing the hole transport layer includes any one or a combination of two or more of the following: vacuum deposition, solution method, and sol-gel method.

10. A perovskite solar cell, characterized in that, Includes the perovskite optoelectronic device structure as described in any one of claims 1-2, as well as the first electrode and the second electrode; The first electrode is electrically connected to the hole transport layer of the perovskite optoelectronic device structure, and the second electrode is electrically connected to the electron transport layer.

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