Solar cells, functional materials and their preparation methods, electrical devices, power generation devices and photovoltaic devices

Abstract

This application discloses a solar cell, a functional material and its preparation method, an electrical device, a power generation device, and a photovoltaic device. The solar cell includes a stacked metal oxide layer, a functional layer, and a light-absorbing layer. The functional layer includes a functional material with a structural formula comprising an Ar group, a first group, and a second group. The first and second groups are directly or indirectly connected to the Ar group. The Ar group includes a functional group with an aromatic ring. The first group includes a carboxyl group or its corresponding salt, and the second group includes a phosphonic acid group or its corresponding salt. By setting a functional layer between the metal oxide layer and the light-absorbing layer, this application improves the surface wettability of the functional layer, allowing the precursor liquid of the light-absorbing material to spread well on the surface of the functional layer. This results in fewer defects at the interface between the light-absorbing layer and the functional layer formed by the precursor liquid, thereby optimizing the photoelectric conversion efficiency and stability of the solar cell.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cell technology, and more particularly to a solar cell, functional materials and preparation methods, electrical devices, power generation devices and photovoltaic devices. Background Technology

[0002] Perovskite solar cells, as third-generation solar cells, utilize perovskite materials as the light-absorbing layer, exhibiting significant performance advantages such as high light absorption coefficient, carrier mobility, and a direct and tunable optical bandgap. Currently, inverted perovskite solar cells use self-assembled monolithic materials as the hole transport layer. However, due to the molecular structure characteristics of these self-assembled materials, the wettability of the perovskite precursor solution on their surface is poor, leading to numerous defects in the grown perovskite layer and consequently, low photoelectric conversion efficiency and poor stability of the solar cell. Summary of the Invention

[0003] In view of the above-mentioned technical problems, this application provides a solar cell, a functional material and a preparation method thereof, an electrical device, a power generation device and a photovoltaic device to improve the photoelectric conversion efficiency and stability of solar cells.

[0004] The first technical solution adopted in this application is: to provide a solar cell, the solar cell comprising a stacked metal oxide layer, a functional layer and a light-absorbing layer, wherein the functional layer comprises a functional material, wherein the functional material comprises an Ar group, at least one first group and at least one second group, wherein the first group and the second group are independently directly or indirectly connected to the Ar group, wherein the Ar group comprises a functional group having an aromatic ring, the first group comprises a carboxyl group or its corresponding salt, and the second group comprises a phosphonic acid group or its corresponding salt.

[0005] In the technical solution of this application embodiment, the solar cell includes a metal oxide layer, a functional layer, and a light-absorbing layer. The functional layer includes a functional material. The functional material has a structural formula including an Ar group, at least one first group, and at least one second group. The first group and the second group are each independently directly or indirectly connected to the Ar group. The first group includes a carboxyl group or its corresponding salt. The second group includes a phosphonic acid group or its corresponding salt. The Ar group includes functional groups with aromatic rings. The Ar group has a conjugated structure, which is beneficial for carrier transport. Phosphonic acid groups or their corresponding salts are more likely to anchor to metal oxides than carboxyl groups or their corresponding salts, enabling the functional material to combine with the metal oxide. At the same time, phosphonic acid groups or their corresponding salts preferentially combine with metal oxides than carboxyl groups or their corresponding salts. Carboxyl groups or their corresponding salts are hydrophilic, which can improve the wettability of the functional layer surface. The precursor liquid of the light-absorbing material is placed on the surface of the functional layer with improved wettability, so that the precursor liquid of the light-absorbing material has good spreadability on the surface of the functional layer. This results in fewer defects at the interface between the light-absorbing layer and the functional layer formed by the precursor liquid, thereby optimizing the photoelectric conversion efficiency and stability of the solar cell.

[0006] In some embodiments, the Ar group is an aromatic or heteroaromatic group having 12 to 30 cyclic carbon atoms.

[0007] In the technical solution of this application embodiment, the Ar group has a conjugated structure, which is beneficial to the transport of charge carriers and improves the photoelectric conversion efficiency and stability of the solar cell.

[0008] In some embodiments, the Ar group includes at least one of the following Ar1 to Ar9 groups, where the dashed lines in the figure represent the connection sites where the Ar group is used to directly or indirectly connect to a hydrogen group, a first group, or a second group:

[0009]

[0010]

[0011] Among them, Y 1 Each group independently includes -CR 1 2-、-NR 1 -, -O-, -S-, -C(=O)-, -C(=CR 1 2) - one or more of them; R 1 Each group independently includes hydrogen groups, halogen groups, and R groups. 1 'R groups, halogen-substituted R 1 'group, -OR 1 '、-OCOR 1 '、-NR 1 '2、-SR1 One or more of the following; R 1 Each group independently includes one or more of the following: substituted or unsubstituted phenyl, thiophene, and alkyl groups having 1 to 10 carbon atoms; n is greater than or equal to 1.

[0012] In the technical solution of this application embodiment, the Ar group has a conjugated structure, which is beneficial to the transport of charge carriers and improves the photoelectric conversion efficiency and stability of the solar cell.

[0013] In some embodiments, the first group or the second group is independently linked to an Ar group via m L groups, where m ranges from 1 to 10, and each L group independently includes -CR 2 2-、-NR 2 -、-O-、-SiR 2 2-、-PR 2 -, -S-, -C(=O)-, -C(=S)-, -C(=NR 2 )-、-C(=CR 2 2) - or one or more of L1 to L8 below, where the dashed part indicates the connection site where the L group is used to connect the Ar group and the connection site for connecting the first group or the second group;

[0014]

[0015] Y 2 Each group independently includes -CR 2 2-、-NR 2 -, -O-, -S-, -C(=O)-, -C(=CR 2 2) - one or more of them; R 2 Each group independently includes hydrogen groups, halogen groups, and R groups. 2 'R groups, halogen-substituted R 2 'group, -OR 2 '、-OCOR 2 '、-NR 2 '2、-SR 2 One or more of the following; R 2 Each of the following groups independently includes one or more of the following: substituted or unsubstituted phenyl, thiophene, and alkyl groups having 1-10 carbon atoms; each of the following groups independently includes -CR 2 =, -N= or one or more of them.

[0016] In the technical solution of this application embodiment, the L group provided above is used as a linking group between the Ar group and the first group or the second group, which is beneficial to the arrangement of functional materials on the surface of metal oxide and the transport of charge carriers in the solar cell, thereby improving the photoelectric conversion efficiency and stability of the solar cell.

[0017] In some embodiments, the L group independently includes -CR 2 2-、-NR 2 -, -O-, -C(=O)- or one or more of the following L9~L11:

[0018]

[0019] In the technical solution of this application embodiment, the L group provided above is used as a linking group between the Ar group and the first group or the second group, which is beneficial to the arrangement of functional materials on the surface of metal oxide and the transport of charge carriers in solar cells, thereby improving the photoelectric conversion efficiency and stability of solar cells.

[0020] In some embodiments, the structural formula of the functional material includes at least two first groups.

[0021] In the technical solution of this application embodiment, the functional material containing at least two first groups improves the wettability of the thin film surface, thereby optimizing the surface defect problem of the light absorption layer and improving the photoelectric conversion efficiency and stability of the solar cell.

[0022] In some embodiments, the structural formula of the functional material includes at least two second groups.

[0023] In the technical solution of this application embodiment, the functional material containing at least two second groups enhances the bonding ability with the metal oxide layer, thereby improving the contact interface between the perovskite and the metal oxide layer, and thus improving the photoelectric conversion efficiency and stability of the solar cell.

[0024] In some embodiments, the cations of the salt corresponding to the carboxyl group and the salt corresponding to the phosphonic acid group include one or more of alkali metal cations, ammonium ions, and organic ammonium cations.

[0025] In the technical solutions of this application embodiment, the cations of the salt corresponding to the carboxyl group and the cations of the salt corresponding to the phosphonic acid group are within the above-mentioned range, which increases the flexibility of the selection of functional materials.

[0026] In some embodiments, the organic ammonium cations each independently comprise substituted or unsubstituted C1-C20 alkylammonium cations, wherein, when the C1-C20 alkylammonium cations are substituted, the substituents each independently comprise one or more of a hydroxyl group, a halogen, or a benzene ring; and / or the alkali metal cations each independently comprise sodium ions (Na+). + ), potassium ions (K) + ), rubidium ions (Rb + ) and cesium ions (Cs + One or more of them.

[0027] In the technical solutions of this application embodiment, the organic ammonium cations and / or alkali metal cations are within the above-mentioned range, which increases the flexibility of the selection of functional materials.

[0028] In some embodiments, the functional material includes one or more of the following SAM1 to SAM8:

[0029]

[0030]

[0031] In the technical solution of this application embodiment, the functional material not only has good bonding with the metal oxide layer, but also the precursor liquid of the light-absorbing material has good spreadability on the surface of the functional layer, thereby reducing the defects at the interface between the light-absorbing layer and the functional layer formed by the precursor liquid, and thus optimizing the photoelectric conversion efficiency and stability of the solar cell.

[0032] In some implementations, the thickness of the functional layer is 0.1 nm to 5 nm.

[0033] In the technical solution of this application embodiment, the thickness of the functional layer is within the above range, which can shorten the transport path of charge carriers in the functional layer, improve the transport efficiency of charge carriers, and improve the photoelectric conversion efficiency and stability of the solar cell.

[0034] In some implementations, the metal oxide layer is the first electrode layer or hole transport layer of the solar cell.

[0035] In the technical solution of this application embodiment, the metal oxide layer contains O atoms, making it easy for the surface of the metal oxide layer to carry hydroxyl groups, which helps to anchor the functional material to its interface and improve device stability. Furthermore, compared to the metal oxide layer being the first electrode layer, when the metal oxide is used as the hole transport layer, the interaction force between the metal oxide layer with more hydroxyl groups and the functional layer material is stronger, thereby improving the stability of the solar cell. In addition, the metal oxide can be used as the hole transport layer alone, but due to the many defects on the surface of the metal oxide, high-valence metal ions will oxidize the perovskite interface it contacts, which will reduce the stability of the solar cell. At the same time, the work function of most metal oxide surfaces does not match the valence band top of perovskite, resulting in a decrease in the photoelectric conversion efficiency of the solar cell. The introduction of functional layer materials can also mitigate the above problems, and can achieve higher photoelectric conversion efficiency and stability of the solar cell.

[0036] In some embodiments, the first electrode layer comprises one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium zinc oxide (IZO); and / or the hole transport layer comprises one or more of nickel oxide, molybdenum oxide, and tungsten oxide.

[0037] In some embodiments, the solar cell is an inverted perovskite solar cell, which includes a first electrode layer, a functional layer, a light-absorbing layer, an electron transport layer, and a second electrode layer stacked sequentially, wherein the first electrode layer is a metal oxide layer; or, the inverted perovskite solar cell includes a first electrode layer, a hole transport layer, a functional layer, a light-absorbing layer, an electron transport layer, and a second electrode layer stacked sequentially, wherein the hole transport layer is a metal oxide layer.

[0038] This application optimizes the buried interface of the light absorption layer by setting a functional layer and combining the functional layer with the metal oxide layer, resulting in fewer defects in the formed light absorption layer, thereby improving the photoelectric conversion efficiency and stability of the solar cell.

[0039] In some embodiments, the light-absorbing layer comprises a perovskite material with the general formula ABX3 or A2CDX6, wherein A comprises inorganic, organic, or mixed organic-inorganic cations, including methylamine cations, ethylamine cations, propylamine cations, butylamine cations, pentamine cations, hexamine cations, formamidin cations, imidazole cations, and Cs. + 、Rb + Li + Na + K + Cu + Ag + Au + or Hg + One or more of the following; B includes inorganic cations, including Pb 2+ Sn 2+ One or more of the following; C includes inorganic or organic or mixed organic-inorganic cations, including Ag. + Cu + Au + FA + GA + D includes inorganic cations, including Bi. 3+ Sb 3+ Cr 3+ Fe 3+ Co 3+ Ga 3+ As 3+ Ru 3+ ,Rh 3+ In 3+ Ir3+ Au 3+ Or Al 3+ One or more of them; X includes inorganic anions, including F - Cl - ,Br - I - SCN - CNO - OCN - OSCN - SH - OH - CN - SeCN - One or more of them.

[0040] The second technical solution adopted in this application is: to provide a functional material, wherein the structural formula of the functional material includes an Ar group, at least one first group and at least one second group, wherein the first group and the second group are each independently directly or indirectly connected to the Ar group, wherein the Ar group includes a functional group having an aromatic ring, the first group includes a carboxyl group or its corresponding salt, and the second group includes a phosphonic acid group or its corresponding salt.

[0041] In the technical solution of this application embodiment, the structural formula of the functional material includes an Ar group, at least one first group, and at least one second group. The first group and the second group are each independently directly or indirectly connected to the Ar group. The first group includes a carboxyl group or its corresponding salt. The second group includes a phosphonic acid group or its corresponding salt. The Ar group includes a functional group with an aromatic ring. The Ar group has a conjugated structure, which is beneficial for carrier transport. The phosphonic acid group or its corresponding salt is more easily anchored to the metal oxide than the carboxyl group or its corresponding salt, allowing the functional material to bind with the metal oxide. Simultaneously, because the phosphonic acid group or its corresponding salt preferentially binds to the metal oxide, the carboxyl group or its corresponding salt faces away from the metal oxide side of the functional layer. The carboxyl group or its corresponding salt is hydrophilic, which can improve the surface wettability of the functional layer. A precursor liquid for the light-absorbing material is placed on the surface of the functional layer with improved wettability, allowing the precursor liquid to spread well on the surface of the functional layer. This results in fewer defects at the interface between the light-absorbing layer and the functional layer formed by the precursor liquid, thereby optimizing the photoelectric conversion efficiency and stability of the solar cell.

[0042] The third technical solution adopted in this application is to provide an electrical device, including the solar cell described above.

[0043] The fourth technical solution adopted in this application is: to provide a power generation device, including the solar cell as described above.

[0044] The fifth technical solution adopted in this application is: to provide a photovoltaic device, including the solar cell as described above.

[0045] Since the apparatus and / or device of this application include the solar cell provided in this application, they have at least the same advantages as solar cells.

[0046] The above description is merely an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0047] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiments below. The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of this application. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0048] Figure 1 This is a schematic diagram of the structure of a solar cell according to an embodiment of this application;

[0049] Figure 2 This is a schematic diagram of the structure of a solar cell according to an embodiment of this application;

[0050] Figure 3 This is a schematic diagram of the structure of an electrical device according to an embodiment of this application;

[0051] Figure 4 This is a schematic diagram of the structure of a power generation device according to an embodiment of this application;

[0052] Figure 5 This is a schematic diagram of the structure of a photovoltaic device according to an embodiment of this application.

[0053] Marker explanation:

[0054] Solar cell 100, first electrode layer 101A, functional layer 102, light absorption layer 103, second electrode layer 104, electron transport layer 105, hole transport layer 101B, metal oxide layer 101, power consumption device 1000, power generation device 2000, photovoltaic device 3000. Detailed Implementation

[0055] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0056] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0057] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0058] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0059] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this document generally indicates that the preceding and following related objects have an "or" relationship.

[0060] In the description of the embodiments of this application, the term "multiple" refers to two or more (including two), similarly, "multiple sets" refers to two or more (including two sets), and "multiple pieces" refers to two or more (including two pieces).

[0061] In related technologies, inverted perovskite solar cells use self-assembled materials as hole transport layers. However, due to the molecular structure characteristics of self-assembled materials, the wettability of the perovskite precursor solution on its surface is poor, resulting in many defects in the grown perovskite layer, leading to low photoelectric conversion efficiency and poor stability of the solar cell.

[0062] Reference Figure 1The first technical solution adopted in this application is: to provide a solar cell 100, which includes a metal oxide layer 101, a functional layer 102 and a light absorption layer 103 stacked together. The functional layer 102 includes a functional material. The functional material has a structural formula including an Ar group, at least one first group and at least one second group. The first group and the second group are each independently directly or indirectly connected to the Ar group. The Ar group includes a functional group having an aromatic ring. The first group includes a carboxyl group or its corresponding salt. The second group includes a phosphonic acid group or its corresponding salt.

[0063] In the technical solution of this application embodiment, the solar cell 100 includes a metal oxide layer 101, a functional layer 102, and a light-absorbing layer 103. The functional layer 102 includes a functional material. The functional material has a structural formula including an Ar group, at least one first group, and at least one second group. The first group and the second group are each independently directly or indirectly connected to the Ar group. The first group includes a carboxyl group or its corresponding salt. The second group includes a phosphonic acid group or its corresponding salt. The Ar group includes functional groups with aromatic rings. The Ar group has a conjugated structure, which is beneficial for carrier transport. Phosphonic acid groups or their corresponding salts are more likely to anchor to metal oxides than carboxyl groups or their corresponding salts, enabling the functional material to combine with the metal oxide. At the same time, phosphonic acid groups or their corresponding salts preferentially combine with metal oxides than carboxyl groups or their corresponding salts. Carboxyl groups or their corresponding salts are hydrophilic, which can improve the surface wettability of the functional layer 102. The precursor liquid of the light-absorbing material is placed on the surface of the functional layer 102 with improved wettability, so that the precursor liquid of the light-absorbing material has good spreadability on the surface of the functional layer 102. This results in fewer defects at the interface between the light-absorbing layer 103 and the functional layer 102 formed by the precursor liquid, thereby optimizing the photoelectric conversion efficiency and stability of the solar cell 100.

[0064] In some embodiments, the Ar group is an aromatic or heteroaromatic group having 12 to 30 cyclic carbon atoms.

[0065] In the technical solution of this application embodiment, the Ar group has a conjugated structure, which is beneficial to the transport of charge carriers and improves the photoelectric conversion efficiency and stability of the solar cell.

[0066] In some embodiments, the Ar group includes at least one of the following Ar1 to Ar9 groups, where the dashed lines in the figure represent the connection sites where the Ar group is used to directly or indirectly connect to a hydrogen group, a first group, or a second group:

[0067]

[0068]

[0069] Among them, Y 1 Each group independently includes -CR 1 2-、-NR 1 -, -O-, -S-, -C(=O)-, -C(=CR 1 2) - one or more of them; R 1 Each group independently includes hydrogen groups, halogen groups, and R groups. 1 'R groups, halogen-substituted R 1 'group, -OR 1 '、-OCOR 1 '、-NR 1 '2、-SR 1 One or more of the following; R 1 Each group independently includes one or more of the following: substituted or unsubstituted phenyl, thiophene, and alkyl groups having 1 to 10 carbon atoms; n is greater than or equal to 1.

[0070] In the technical solution of this application embodiment, the value of n can be 0, 1, 2, 3, or 4, or a range of any two of the above values, for example, 0 to 2, 1 to 4, 2 to 4, etc. The Ar group has a conjugated structure, which is beneficial to the transport of charge carriers and improves the photoelectric conversion efficiency and stability of the solar cell 100.

[0071] In some embodiments, the first group or the second group is independently linked to an Ar group via m L groups, where m ranges from 1 to 10, and each L group independently includes -CR 2 2-、-NR 2 -、-O-、-SiR 2 2-、-PR 2 -, -S-, -C(=O)-, -C(=S)-, -C(=NR 2 )-、-C(=CR 2 2) - or one or more of L1 to L8 below, where the dashed part indicates the connection site where the L group is used to connect the Ar group and the connection site for connecting the first group or the second group;

[0072]

[0073] Y 2 Each group independently includes -CR 2 2-、-NR 2 -, -O-, -S-, -C(=O)-, -C(=CR 2 2) - one or more of them; R 2 Each group independently includes hydrogen groups, halogen groups, and R groups. 2 'R groups, halogen-substituted R 2'group, -OR 2 '、-OCOR 2 '、-NR 2 '2、-SR 2 One or more of the following; R 2 Each of the following groups independently includes one or more of the following: substituted or unsubstituted phenyl, thiophene, and alkyl groups having 1-10 carbon atoms; each of the following groups independently includes -CR 2 =, -N= or one or more of them.

[0074] In the technical solution of this application embodiment, the value of m can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or a range of any two of the above values, for example, it can be 1 to 5, 2 to 8, 3 to 10, etc.

[0075] In the technical solution of this application embodiment, the L group provided above is used as a linking group between the Ar group and the first group or the second group, which is beneficial to the arrangement of functional materials on the surface of metal oxide and the transport of charge carriers in the solar cell 100, thereby improving the photoelectric conversion efficiency and stability of the solar cell 100.

[0076] In some embodiments, the L group independently includes -CR 2 2-、-NR 2 -, -O-, -C(=O)- or one or more of the following L9~L11:

[0077]

[0078] In the technical solution of this application embodiment, the L group provided above is used as a linking group between the Ar group and the first group or the second group, which is beneficial to the arrangement of functional materials on the surface of metal oxide and the transport of charge carriers in the solar cell 100, thereby improving the photoelectric conversion efficiency and stability of the solar cell 100.

[0079] In some embodiments, the structural formula of the functional material includes at least two first groups.

[0080] In the technical solution of this application embodiment, the functional material containing at least two first groups improves the wettability of the thin film surface, thereby optimizing the surface defect problem of the light absorption layer 103 and improving the photoelectric conversion efficiency and stability of the solar cell 100.

[0081] In some embodiments, the structural formula of the functional material includes at least two second groups.

[0082] In the technical solution of this application embodiment, the functional material containing at least two second groups enhances the bonding ability with the metal oxide layer 101, thereby improving the contact interface between the perovskite and the metal oxide layer 101, and thus improving the photoelectric conversion efficiency and stability of the solar cell 100.

[0083] In some embodiments, the cations of the salt corresponding to the carboxyl group and the salt corresponding to the phosphonic acid group include one or more of alkali metal cations, ammonium ions, and organic ammonium cations.

[0084] In the technical solutions of this application embodiment, the cations of the salt corresponding to the carboxyl group and the cations of the salt corresponding to the phosphonic acid group are within the above-mentioned range, which increases the flexibility of the selection of functional materials.

[0085] In some embodiments, the organic ammonium cations each independently comprise substituted or unsubstituted C1-C20 alkylammonium cations, wherein, when the C1-C20 alkylammonium cations are substituted, the substituents each independently comprise one or more of a hydroxyl group, a halogen, or a benzene ring; and / or the alkali metal cations each independently comprise sodium ions (Na+). + ), potassium ions (K) + ), rubidium ions (Rb + ) and cesium ions (Cs + One or more of them.

[0086] In the technical solutions of this application embodiment, the organic ammonium cations and / or alkali metal cations are within the above-mentioned range, which increases the flexibility of the selection of functional materials.

[0087] In some embodiments, the functional material includes one or more of the following SAM1 to SAM8:

[0088]

[0089]

[0090] In the technical solution of this application embodiment, the functional material not only has good bonding with the metal oxide layer 101, but also the precursor liquid of the light-absorbing material has good spreadability on the surface of the functional layer 102, thereby reducing the defects at the interface between the light-absorbing layer 103 and the functional layer 102 formed by the precursor liquid, thus optimizing the photoelectric conversion efficiency and stability of the solar cell 100.

[0091] In some embodiments, the thickness of the functional layer 102 is 0.1 nm to 5 nm. For example, the thickness of the functional layer can be 0.1 nm, 0.12 nm, 0.2 nm, 0.25 nm, 0.3 nm, 0.35 nm, 0.4 nm, 0.45 nm, 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm, etc., or a range of any two of the above values, such as 0.1 nm to 2 nm, 2 nm to 4 nm, 4 nm to 5 nm, etc.

[0092] In the technical solution of this application embodiment, the thickness of the functional layer 102 is within the above range, which can shorten the transport path of charge carriers in the functional layer 102, improve the transport efficiency of charge carriers, and improve the photoelectric conversion efficiency and stability of the solar cell 100.

[0093] In some embodiments, the metal oxide layer 101 is the first electrode layer 101A or the hole transport layer 101B of the solar cell 100.

[0094] In the technical solution of this application embodiment, the metal oxide layer 101 contains O atoms, making it easy for the surface of the metal oxide layer 101 to carry hydroxyl groups, which helps to anchor the functional material to its interface and improve device stability. Furthermore, compared to the case where the metal oxide layer 101 is the first electrode layer 101A and the metal oxide is the hole transport layer 101B, the interaction force between the metal oxide layer 101 with more hydroxyl groups and the functional layer 102 material is stronger, thereby improving the stability of the solar cell 100. In addition, the metal oxide 101 can be used alone as the hole transport layer 101B, but due to the numerous defects on the surface of the metal oxide, high-valence metal ions will oxidize the perovskite interface it contacts, reducing the stability of the solar cell 100. At the same time, the work function of most metal oxide surfaces does not match the valence band top of the perovskite, leading to a decrease in the photoelectric conversion efficiency of the solar cell 100. The introduction of the functional layer 102 material can further mitigate the above problems, achieving higher photoelectric conversion efficiency and stability of the solar cell 100.

[0095] In some embodiments, solar cell 100 is an inverse perovskite solar cell. See also... Figure 1 The inverted perovskite solar cell 100 includes a first electrode layer 101A, a functional layer 102, a light-absorbing layer 103, an electron transport layer 105, and a second electrode layer 104, which are sequentially stacked. The first electrode layer 101A is a metal oxide layer 101; or, please refer to [link to relevant documentation]. Figure 2The inverted perovskite solar cell 100 includes a first electrode layer 101A, a hole transport layer 101B, a functional layer 102, a light absorption layer 103, an electron transport layer 105, and a second electrode layer 104 stacked sequentially. The hole transport layer 101B is a metal oxide layer 101.

[0096] This application optimizes the buried interface of the light absorption layer 103 by setting a functional layer 102 and combining the functional layer 102 with the metal oxide layer 101, resulting in fewer defects in the formed light absorption layer 103, thereby improving the photoelectric conversion efficiency and stability of the solar cell 100.

[0097] In some embodiments, the first electrode layer 101A includes, but is not limited to, the following materials: fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), etc., with a thickness of 10 nm to 1000 nm. For example, the thickness of the first electrode layer 101A can be 10 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, etc., or a range consisting of any two of the above values, for example, 10 nm to 300 nm, 300 nm to 500 nm, 400 nm to 800 nm, 600 nm to 1000 nm, etc.

[0098] In some embodiments, the hole transport layer 101B includes, but is not limited to, the following materials: nickel oxide, molybdenum oxide, tungsten oxide, etc., with a thickness of 10nm to 100nm. For example, the thickness of the hole transport layer 101B can be 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, etc., or a range consisting of any two of the above values, such as 10nm to 30nm, 30nm to 50nm, 40nm to 80nm, 60nm to 100nm, etc.

[0099] In some embodiments, the light-absorbing layer 103 comprises a perovskite material with the general formula ABX3 or A2CDX6, wherein A comprises at least one inorganic or organic monovalent cation, B comprises at least one inorganic divalent cation, C comprises at least one inorganic monovalent cation, D comprises at least one inorganic trivalent cation, and X comprises at least one monovalent anion. Exemplarily, the organic monovalent cation comprises (NR1R2R3R4). +(R1R2N=CR3R4) + (R1R2N-C(R5)=NR3R4) + and (R1R2N-C(NR5R6)=NR3R4) + One or more of them, wherein R1, R2, R3, R4, R5 and R6 are each independently selected from H, substituted or unsubstituted C1 to C6. 20 Alkyl, or substituted or unsubstituted aryl groups. Optionally, the organic monovalent cation includes (H₂N=CH-NH₂). + (abbreviated as FA), CH3NH3 + (abbreviated as MA), one or more of the following: ethylamine cation, propylamine cation, butylamine cation, pentamine cation, hexamine cation, and imidazole cation. For example, inorganic monovalent cations include: Li + Na + K + 、Rb + Cs + Cu + Ag + Au + or Hg + At least one of the following. Exemplarily, the inorganic divalent cation includes: Pb 2+ Sn 2+ Be 2+、 Mg 2+ Ca 2+ 、Sr 2 + Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ Cd 2+ Cu 2+ Mn 2+ Pd 2+ Yb 2+ Or Eu 2+ At least one of them, Pb 2+ Sn 2+ One or two of them. For example, inorganic trivalent cations include: Bi 3+ Sb 3+ Cr 3+ Fe 3+ Co 3+ Ga 3+ As 3+ Ru 3+ ,Rh 3+ In 3+ Ir3+ Ni 3+ Au 3+ Or Al 3+ At least one of the following. For example, a monovalent anion includes: F - Cl - ,Br - I - SCN - CNO - OCN - OSCN - SH - CN - SeCN - At least one of them, C1, can be selected. - ,Br - I - One or more of them.

[0100] The light-absorbing layer 103 has a band gap of 1.20 eV to 2.30 eV and a thickness of 200 nm to 1000 nm. For example, the thickness of the light-absorbing layer 103 can be 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, etc., or any range of two of the above values, such as 200 nm to 300 nm, 300 nm to 500 nm, 400 nm to 800 nm, 600 nm to 1000 nm, etc.

[0101] In some embodiments, the electron transport layer 105 includes, but is not limited to, at least one of the following materials and their derivatives, as well as materials obtained by doping or passivation: methyl [6,6]-phenyl C61 butyrate (PC61BM), methyl [6,6]-phenyl C71 butyrate (PC71BM), fullerene C60 (C60), fullerene C70 (C70), tin dioxide (SnO2), zinc oxide (ZnO), perylene imide (PDI) materials, naphthalene imide (NDI) materials, etc., with a thickness of 5 nm to 100 nm. For example, the thickness of the electron transport layer 105 can be 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, etc., or a range of any two of the above values, such as 5nm~30nm, 30nm~50nm, 40nm~80nm, 60nm~100nm, etc.

[0102] In some embodiments, the material of the second electrode layer 104 is an organic, inorganic, or organic-inorganic conductive material, including but not limited to the following materials: Ag, Cu, C, Au, Al, ITO, AZO, BZO, IZO, etc., with a thickness of 10nm to 1000nm. For example, the thickness of the second electrode layer 104 can be 10nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, etc., or a range consisting of any two of the above values, for example, 10nm to 300nm, 300nm to 500nm, 400nm to 800nm, 600nm to 1000nm, etc.

[0103] In some embodiments, the solar cell further includes a substrate layer disposed on the side of the first electrode layer 101A away from the light-absorbing layer 103 for supporting the solar cell. The substrate layer may be, but is not limited to, a glass substrate or a flexible substrate. In some embodiments, the material of the flexible substrate layer may be, for example (but not limited to), an organic polymer material, and further, may be a mixture of one or more of the following materials in different proportions: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), etc.

[0104] The second technical solution adopted in this application is: to provide a functional material, wherein the structural formula of the functional material includes an Ar group, at least one first group and at least one second group, wherein the first group and the second group are each independently directly or indirectly connected to the Ar group, wherein the Ar group includes a functional group having an aromatic ring, the first group includes a carboxyl group or its corresponding salt, and the second group includes a phosphonic acid group or its corresponding salt.

[0105] In the technical solution of this application embodiment, the structural formula of the functional material includes an Ar group, at least one first group, and at least one second group. The first group and the second group are each independently directly or indirectly connected to the Ar group. The first group includes a carboxyl group or its corresponding salt. The second group includes a phosphonic acid group or its corresponding salt. The Ar group includes a functional group with an aromatic ring. The Ar group has a conjugated structure, which is beneficial for carrier transport. The phosphonic acid group or its corresponding salt is more easily anchored to the metal oxide than the carboxyl group or its corresponding salt, allowing the functional material to bind with the metal oxide. Simultaneously, the phosphonic acid group or its corresponding salt preferentially binds to the metal oxide than the carboxyl group or its corresponding salt. The carboxyl group or its corresponding salt is hydrophilic, which can improve the surface wettability of the functional layer 102. A precursor liquid for the light-absorbing material is applied to the surface of the functional layer 102 with improved wettability, resulting in good spreadability of the precursor liquid on the surface of the functional layer 102. This reduces the defects at the interface between the light-absorbing layer 103 and the functional layer 102 formed by the precursor liquid, thereby optimizing the photoelectric conversion efficiency and stability of the solar cell 100.

[0106] When using the functional materials provided in this application, the functional materials can be directly dissolved in an organic solvent and coated onto the surface of a metal oxide by spin coating, spraying, blade coating, slot coating, or roll-to-roll printing. Alternatively, a substrate containing a metal oxide or a metal oxide substrate can be immersed in a precursor solution, and the functional materials self-assemble on the metal oxide surface to form a monolayer. The solvent can be one or more of methanol, isopropanol, ethanol, and chlorobenzene, with a concentration of 0.1 mg / mL to 10 mg / mL. The thickness of the functional materials on the metal oxide surface can be 0.1 nm to 5 nm. After the functional materials are prepared on the metal oxide surface, the solvent can be removed by annealing or vacuum to form the functional layer 102.

[0107] Reference Figure 3 This application also provides an electrical device 1000, including the solar cell 100 as described above.

[0108] In this application, the solar cell 100 serves as the power source for the aforementioned electrical device 1000; alternatively, the solar cell 100 can serve as an energy storage unit for the aforementioned electrical device 1000. As an example, the electrical device 1000 can be a lighting element, a display element, or an automobile, etc.

[0109] Reference Figure 4 This application also provides a power generation device 2000, including the solar cell 100 as described above.

[0110] The solar cell 100 disclosed in this application can be used in a power-consuming device 1000 or a power-generating device 2000 that applies photoelectric conversion. The power-consuming device 1000 can be, but is not limited to, mobile phones, tablets, laptops, electric toys, power tools, electric vehicles, electric cars, ships, spacecraft, etc. Electric toys can include stationary or mobile electric toys, such as game consoles, electric car toys, electric ship toys, and electric airplane toys, etc. Spacecraft can include airplanes, rockets, space shuttles, and spacecraft, etc. The power-generating device 2000 can include a solar cell and an energy storage device, which can be a secondary battery.

[0111] refer to Figure 5 This application also provides a photovoltaic device 3000, including the solar cell 100 as described above.

[0112] To make the technical problems, technical solutions, and beneficial effects solved by the embodiments of this application clearer, the following will provide a more detailed description in conjunction with the embodiments and accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit this application or its applications. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0113] The features and performance of this application will be further described in detail below with reference to the embodiments.

[0114] Example 1

[0115] (1) Take 20 pieces of FTO conductive glass with a size of 2.0cm×2.0cm, and remove 0.35cm of FTO from each end by laser etching, with a thickness of about 500nm, exposing the glass substrate;

[0116] (2) Use water, acetone and isopropanol to ultrasonically clean the etched FTO conductive glass several times in sequence.

[0117] (3) The FTO conductive glass was dried under a nitrogen gun and then further cleaned in an ultraviolet ozone generator.

[0118] (4) A methanol solution of nano-nickel oxide with a concentration of 10 mg / mL was spin-coated onto the surface of FTO conductive glass at 2000 rpm, and the solvent was removed by vacuum or annealing to form a 30 nm nickel oxide film.

[0119] (5) Dissolve the functional material SAM1 in methanol (0.3 mg / mL) to obtain a functional material solution; spin-coat the functional material solution on the surface of the nickel oxide film at 3000 rpm, and obtain a 5 nm thick functional layer 102 by vacuuming or annealing.

[0120] (6) Weigh out lead iodide (726 mg), formamidine iodide (240 mg), cesium iodide (19 mg), and lead bromide (11 mg) and dissolve them in 1 mL of a DMF:DMSO mixed solvent with a volume ratio of 4:1. Stir for 3 h, filter through a 0.22 μm organic filter membrane to obtain a perovskite precursor solution. Spin-coat the perovskite precursor solution onto the obtained functional layer 102 at 3000 rpm, anneal at 100 °C for 30 min, and cool to room temperature. The structural formula of the perovskite material in the light absorption layer 103 is Cs. 0.05 FA 0.95 PbBr 0.15 I 2.85 The thickness of the light absorption layer 103 is 900 nm.

[0121] (7) Electron transport material PC was spin-coated onto the light-absorbing layer 103 at 1500 rpm. 61 BM was annealed at 100°C for 10 min to form an electron transport layer 105 with a thickness of 35 nm. Then, its passivation material BCP was spin-coated at 5000 rpm to form a barrier layer with a thickness of 15 nm.

[0122] (8) Place the obtained wafer into a vapor deposition machine and vapor deposit Cu electrode with a thickness of 80 nm to obtain a battery device labeled as Battery 1.

[0123] The preparation method of the functional material SAM1 is as follows:

[0124] Procedure 1: Compound 1 (1 mmol), Compound 2 (1 mmol), Compound 3 (2 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 10% mmol), toluene (30 mL), and potassium carbonate aqueous solution (2 M, 10 mL) were mixed and heated at 110 °C for 48 hours under nitrogen protection. After separation by silica gel chromatography, compound 4 was obtained in approximately 36% yield. 1 H NMR(400MHz,DMSO-d6)δ7.64-7.57(m,12H),7.38-7.32(m,12H),4.22-4.19(m,8H),4.02-3.98(m,2 H),2.87-2.79(m,6H),2.56-2.53(m,2H),2.13-2.10(m,4H),1.38-1.36(m,12H),1.10-1.07(m,3H).

[0125]

[0126] Procedure 2: Compound 4 (1 mmol) was mixed with tributylbromosilane (TMSBr, 1.5 mL) and 1,4-dioxane (20 mL) under nitrogen protection and stirred at room temperature for 20 hours. The solvent was removed, and methanol (10 mL) was added and stirred for 12 hours. Deionized water (1 mL) was then added, precipitating a solid powder to obtain SAM1 with a yield of approximately 68%. 1 H NMR(400MHz,DMSO-d6)δ12.01(s,1H),7.63-7.54(m,12H),7.39-7.28(m,1 2H),4.81(s,4H),2.83-2.72(m,6H),2.54-2.51(m,2H),2.03-1.99(m,4H).

[0127]

[0128] Example 2

[0129] Similar to Example 1, the difference is:

[0130] The functional material SAM1 in step (5) of Example 1 is changed to the functional material SAM2. The resulting battery device is labeled as battery 2.

[0131] The preparation method of the functional material SAM2 is as follows:

[0132] Procedure 1: Compound 5 (1 mmol), compound 3 (2.4 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 10% mmol), toluene (30 mL), and potassium carbonate aqueous solution (2 M, 10 mL) were mixed and heated at 110 °C for 48 hours under nitrogen protection. After separation by silica gel chromatography, compound 6 was obtained in approximately 58% yield. 1 H NMR (400MHz, DMSO-d6) δ11.66(s,1H),7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2Hz,2H),7.64(d,J=7. 2Hz, 4H), 7.30 (d, J = 7.2Hz, 4H), 4.22-4.19 (m, 8H), 2.87-2.83 (m, 4H), 2.13-2.10 (m, 4H), 1.38-1.36 (m, 12H).

[0133]

[0134] Procedure 2: Compound 6 (1 mmol), compound 2 (1.2 mmol), tris(dibenzylacetone)dipalladium (0) (Pd2(dba)3, 5% mmol), sodium tert-butoxide (t-BuONa, 5 mmol), 1,1-binaphthyl-2,2-bis(diphenylphosphine) (BINAP, 10% mmol), and toluene (30 mL) were mixed and heated at 110 °C for 48 hours under nitrogen protection. The mixture was then separated by silica gel chromatography to obtain compound 7 in approximately 48% yield. 1 H NMR (400MHz, DMSO-d6) δ7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2Hz,2H),7.64(d,J=7.2Hz,4H),7.61(d,J=7.2Hz,2H),7.30(d,J=7.2 Hz,6H),4.22-4.19(m,8H),4.02-4.00(m,2H),2.87-2.79(m,6H),2.52- 2.49(m,2H),2.13-2.10(m,4H),1.38-1.36(m,12H),1.07-1.04(m,3H).

[0135]

[0136] Procedure 3: Compound 7 (1 mmol) was mixed with tributylbromosilane (TMSBr, 1.5 mL) and 1,4-dioxane (20 mL) under nitrogen protection and stirred at room temperature for 20 hours. The solvent was removed, and methanol (10 mL) was added and stirred for 12 hours. Deionized water (1 mL) was then added, precipitating a solid powder to obtain SAM2 with a yield of approximately 61%. 1 H NMR (400MHz, DMSO-d6) δ12.01(s,1H),7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2Hz,2H),7.64(d,J=7.2Hz,4H ),7.61(d,J=7.2Hz,2H),7.30(d,J=7.2Hz,6H),4.81(s,4H),2.83-2.72(m,6H),2.54-2.51(m,2H),2.03-1.99(m,4H).

[0137]

[0138] Example 3

[0139] Similar to Example 1, the difference is:

[0140] The functional material SAM1 in step (5) of Example 1 is changed to the functional material SAM3. The resulting battery device is labeled as battery 3.

[0141] The preparation method of the functional material SAM3 is as follows:

[0142] Procedure 1: Compound 8 (1 mmol), compound 9 (1.2 mmol), potassium carbonate (5 mmol), and N,N-dimethylformamide (DMF, 10 mL) were mixed and heated at 110 °C for 48 hours under nitrogen protection. After separation by silica gel chromatography, compound 10 was obtained in approximately 88% yield. 1 H NMR(400MHz,DMSO-d6)δ7.19-7.14(m,6H),6.96-6.93(m,2H),4.26(s,2H),4.03-4.00(m,2H), 3.92-3.90(m,2H),2.37-2.33(m,2H),1.43-1.40(m,2H),1.27-1.24(m,2H),1.08-1.06(m,3H).

[0143]

[0144] Procedure 2: Compound 10 (1 mmol), sodium hydride (5 mmol), and N,N-dimethylformamide (10 mL) were mixed and stirred at room temperature for 2 h under nitrogen protection. Then, compound 11 (5.5 mmol) was added dropwise. After heating at 70 °C for 24 h under nitrogen protection, compound 12 was obtained by separation by silica gel chromatography column, with a yield of approximately 23%. 1 H NMR(400MHz,DMSO-d6)δ7.19-7.14(m,6H),6.96-6.93(m,2H),4.18-4.16(m,4H),4.03-4.00(m,2H),3.92-3 .90(m,2H),2.37-2.33(m,2H),1.82-1.77(m,8H),1.43-1.36(m,8H),1.29-1.24(m,10H),1.08-1.06(m,3H).

[0145]

[0146] Procedure 3: Compound 12 (1 mmol) was mixed with tributylbromosilane (TMSBr, 1.5 mL) and 1,4-dioxane (20 mL). The mixture was stirred at room temperature under nitrogen protection for 20 hours. The solvent was removed, and methanol (10 mL) was added and stirred for 12 hours. Deionized water (1 mL) was then added, precipitating a solid powder to obtain SAM3 with a yield of approximately 61%.1 H NMR(400MHz,DMSO-d6)δ12.01(s,1H),7.19-7.14(m,6H),6.96-6.93(m,2H),4.83(s,4H),4.03-4.00(m ,2H),3.92-3.90(m,2H),2.37-2.33(m,2H),1.82-1.77(m,8H),1.43-1.39(m,2H),1.29-1.24(m,10H).

[0147]

[0148] Example 4

[0149] Similar to Example 1, the difference is:

[0150] The functional material SAM1 in step (5) of Example 1 is changed to the functional material SAM4. The resulting battery device is labeled as battery 4.

[0151] The preparation method of the functional material SAM4 is as follows:

[0152] Procedure 1: Compound 5 (1 mmol), compound 2 (2.4 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 10% mmol), toluene (30 mL), and potassium carbonate aqueous solution (2 M, 10 mL) were mixed and heated at 110 °C for 48 hours under nitrogen protection. After separation by silica gel chromatography, compound 13 was obtained in approximately 58% yield. 1 H NMR (400MHz, DMSO-d6) δ11.66(s,1H),7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2Hz,2H),7.64(d,J=7 .2Hz,4H),7.30(d,J=7.2Hz,4H),4.02-3.99(m,4H),2.87-2.83(m,4H),2.13-2.10(m,4H),1.08-1.06(m,6H).

[0153]

[0154] Procedure 2: Compound 13 (1 mmol), compound 14 (1.2 mmol), tris(dibenzylacetone)dipalladium (0) (Pd2(dba)3, 5% mmol), sodium tert-butoxide (t-BuONa, 5 mmol), 1,1-binaphthyl-2,2-bis(diphenylphosphine) (BINAP, 10% mmol), and toluene (30 mL) were mixed and heated at 110 °C for 48 hours under nitrogen protection. The mixture was then separated by silica gel chromatography to obtain compound 7 in approximately 48% yield. 1 H NMR(400MHz, DMSO-d6)δ7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2H z,2H),7.64(s,2H),7.61(d,J=7.2Hz,4H),7.30(d,J=7.2Hz,4H),7.01(s,1 H),4.22-4.19(m,8H),4.19-4.16(m,8H),4.02-4.00(m,4H),3.03(s,4H),2 .87-2.79(m,4H),2.52-2.49(m,4H),1.38-1.36(m,12H),1.07-1.04(m,6H).

[0155]

[0156] Procedure 3: Compound 15 (1 mmol) was mixed with tributylbromosilane (TMSBr, 1.5 mL) and 1,4-dioxane (20 mL). The mixture was stirred at room temperature under nitrogen protection for 20 hours, then the solvent was removed. Methanol (10 mL) was added and stirred for 12 hours. Deionized water (1 mL) was then added, precipitating a solid powder to obtain SAM4, with a yield of approximately 75%. 1 H NMR (400MHz, DMSO-d6) δ12.04(s,2H),7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2Hz,2H),7.64(s,2H),7.61( d,J=7.2Hz,4H),7.30(d,J=7.2Hz,4H),7.01(s,1H),4.83(s,4H),3.03(s,4H),2.87-2.79(m,4H),2.52-2.49(m,4H).

[0157]

[0158] Example 5

[0159] Similar to Example 1, the difference is:

[0160] The functional material SAM1 in step (5) of Example 1 is changed to the functional material SAM5. The resulting battery device is labeled as battery 5.

[0161] The preparation method of the functional material SAM5 is as follows:

[0162] Procedure 1: Compound 13 (1 mmol), compound 16 (10 mL), 50% potassium hydroxide aqueous solution (KOH(aq), 5 mL), and tetrabutylammonium bromide (TBAB, 5% mmol) were mixed and heated at 70°C for 20 hours under nitrogen protection. After separation by silica gel chromatography, compound 17 was obtained with a yield of approximately 88%. 1 H NMR (400MHz, DMSO-d6) δ7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2Hz,2H),7.64(s,2H),7.61(d,J=7.2Hz,4H),7.30(d,J =7.2Hz,4H),4.03-3.99(m,6H),3.22-3.19(m,4H),2.87-2.83(m,4H),2.34-2.30(m,1H),2.13-2.10(m,4H),1.08-1.06(m,6H).

[0163]

[0164] Procedure 2: Compound 10 (1 mmol) and triethyl phosphite (P(OEt)3, 10 mL) were mixed and heated at 180 °C for 12 hours under nitrogen protection. Triethyl phosphite was then removed by vacuum distillation. The crude product was mixed with tributylbromosilane (TMSBr, 2.4 mL) and 1,4-dioxane (5 mL). The mixture was stirred at room temperature under nitrogen protection for 20 hours to remove the solvent. Methanol (5 mL) was added and stirred for 12 hours. Deionized water (1 mL) was added, precipitating a solid powder. After filtration and washing, SAM3 was obtained with a yield of approximately 38%. 1 H NMR (400MHz, DMSO-d6) δ12.03(s,2H),7.96(d,J=7.2Hz,2H),7.88(s,2H),7.74(d,J=7.2Hz,2H),7.64(s,2H),7.61(d,J=7 .2Hz,4H),7.30(d,J=7.2Hz,4H),4.88(s,4H),4.03-4.01(m,2H),2.77-2.73(m,4H),2.54-2.50(m,4H),1.68-1.62(m,5H).

[0165]

[0166] Example 6

[0167] Similar to Example 1, the difference is:

[0168] The functional material SAM1 in step (5) of Example 1 is changed to the functional material SAM6. The resulting battery device is labeled as battery 6.

[0169] The preparation method of the functional material SAM6 is as follows:

[0170] Similar to the synthesis in Example 2, except that:

[0171] Procedure 2: Compound 2 in Example 2 was replaced with compound 17, resulting in SAM6 with an overall yield of 13%. 1 HNMR(400MHz,DMSO-d6)δ12.81(s,1H),8.32(d,J=7.2Hz,2H),7.99-7.86(m,6H),7.78(d,J=7.2Hz,2 H),7.64(d,J=7.2Hz,4H),7.30(d,J=7.2Hz,4H),4.81(s,4H),2.83-2.72(m,4H),2.03-1.99(m,4H).

[0172]

[0173] Example 7

[0174] Similar to Example 1, the difference is:

[0175] The functional material SAM1 in step (5) of Example 1 is changed to the functional material SAM7. The resulting battery device is labeled as battery 7.

[0176] The preparation method of the functional material SAM7 is as follows:

[0177] Similar to the synthesis in Example 1, except that:

[0178] Procedure 1: Compound 1 from Example 1 was replaced with compound 18, and the amount of compound 3 from Example 1 was reduced to 1 mmol, ultimately yielding SAM7 with an overall yield of 21%. 1 H NMR(400MHz,DMSO-d6)δ12.01(s,1H),7.63-7.53(m,8H),7.39-7.23(m,10H),7.08- 7.00(m,3H),4.81(s,2H),2.83-2.72(m,4H),2.54-2.51(m,2H),2.03-1.99(m,2H).

[0179]

[0180] Example 8

[0181] Similar to Example 1, the difference is:

[0182] The functional material SAM1 in step (5) of Example 1 is changed to the functional material SAM8. The resulting battery device is labeled as battery 8.

[0183] The preparation method of the functional material SAM8 is as follows:

[0184] SAM1 (0.1 mmol) and sodium tert-butoxide (t-BuONa, 1 mmol) were dissolved in ethanol (30 mL), stirred at 50 °C for 6 h, concentrated to 5 mL, and then introduced into 50 mL of water to precipitate the precipitate. The precipitate was obtained by filtration, yielding SAM8 with a yield of 87%. 1 H NMR (400MHz, DMSO-d6) δ7.63-7.54(m,12H),7.39-7.28(m,12H),2.83-2.72(m,6H),2.54-2.51(m,2H),2.03-1.99(m,4H).

[0185]

[0186] Example 9

[0187] Similar to Example 1, the difference is:

[0188] Step (4) of Example 1 is removed, and a functional layer 102 is directly formed on the FTO surface, wherein the functional material is SAM1, and the resulting battery device is labeled as battery 9.

[0189] Comparative Example 1

[0190] Similar to Example 1, the difference is:

[0191] The functional material SAM1 was not spin-coated in step (5) of Example 1. The resulting battery device is labeled as Battery 10.

[0192] Comparative Example 2

[0193] Similar to Example 1, the difference is:

[0194] Step (5) in Example 1 is modified to spin-coating functional material D1. The battery device is marked as battery 11.

[0195] Comparative Example 3

[0196] Similar to Example 1, the difference is:

[0197] Step (5) in Example 1 is modified to spin-coating functional material D2. The battery device is identified as battery 12.

[0198] Battery performance tests were conducted on the battery devices 1 to 12 obtained from Examples 1 to 9 and Comparative Examples 1 to 3, and the results are shown in Table 1.

[0199] Test method:

[0200] 1. Photoelectric conversion efficiency test

[0201] The perovskite solar cell test (IV test) uses the Guangyan solar simulator, which conforms to the national standard IEC61215. The light intensity is corrected using a crystalline silicon solar cell to achieve a solar intensity of AM1.5. The cell is connected to a digital source meter, and its photoelectric conversion efficiency is measured under illumination.

[0202] The photoelectric conversion efficiency is calculated as follows:

[0203] PCE = Pout / Pin

[0204] =Voc×Jsc×[(Vmpp×Jmpp) / (Voc×Jsc)] / Pin

[0205] =Voc×Jsc×FF / Pin

[0206] Among them, Pout, Pin, Voc, Jsc, Vmpp, Jmpp, and FF are the battery's operating output power, incident light power, open-circuit voltage, short-circuit current, maximum power point voltage, maximum power point current, and fill factor, respectively. Voc, Jsc, Vmpp, Jmpp, and FF are measured using a digital multimeter.

[0207] Table 1

[0208]

[0209] As can be seen from Table 1, Examples 1-9 and Comparative Examples 1-3, the solar cell devices 1-9 of Examples 1-9 all used the functional materials provided in this application. Their photoelectric conversion efficiency and stability are higher than those of the battery devices 10-12 of Comparative Examples 1-3 that did not use the functional materials provided in this application. This shows that using the functional materials specified in this application can improve the photoelectric conversion efficiency and stability of the solar cell 100.

[0210] Furthermore, as can be seen from Examples 1-9 and Comparative Examples 2-3, after using the functional materials provided in this application, the contact angle of water on the surface of the functional layer 102 is smaller, indicating that it is beneficial to the spreading of the perovskite precursor liquid.

[0211] The method for testing the contact angle is as follows:

[0212] (1) Focusing. Fix the injector or microsyringe above the stage, adjust the camera focus, and then rotate the knob on the back of the camera base to adjust the distance between the camera and the stage so that the image is clearest.

[0213] (2) Add sample. Dispense 0.6 μL to 1.0 μL of deionized water using a microsyringe. At this point, a clear small droplet can be seen at the bottom of the syringe in the moving image.

[0214] (3) Sample reception. Rotate the knob on the stage base to make the stage slowly rise, touch the droplet suspended at the bottom of the injector and then fall down, leaving the droplet on the solid plane. The solid plane is the surface of the functional layer 102 of the intermediate product obtained at the end of step (5).

[0215] (4) Freeze the image. After the sample is captured, click the freeze image button in the upper right corner of the interface within 20 seconds to fix the image. Then click Save as in the File menu to save the image to the folder.

[0216] (5) Angle Measurement. Click the Angle Measurement button to enter the Angle Measurement main interface, press the Start button to open the previously saved image. At this time, a measuring ruler consisting of two straight lines intersecting at a 45-degree angle will appear on the image. Use the Z, X, Q, and A keys on the keyboard, i.e., the left, right, up, and down keys, to adjust the position of the measuring ruler: First, make the measuring ruler tangent to the edge of the droplet, then move the measuring ruler down so that the intersection point is at the top of the droplet, and then use the < and > keys on the keyboard, i.e., the left and right rotation keys, to rotate the measuring ruler until it intersects with the left end of the droplet, thus obtaining the value of the contact angle.

[0217] The above description is merely an embodiment of this application and does not limit the patent scope of this application. Any equivalent structural or procedural transformations made using the content of this application's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of this application.

Claims

1. A solar cell, characterized in that, The solar cell includes a stacked metal oxide layer, a functional layer, and a light-absorbing layer. The functional layer includes a functional material. The functional material has a structural formula including an Ar group, at least one first group, and at least one second group. The first group and the second group are each independently directly or indirectly connected to the Ar group. The Ar group includes a functional group having an aromatic ring. The first group includes a carboxyl group or its corresponding salt, and the second group includes a phosphonic acid group or its corresponding salt.

2. The solar cell as described in claim 1, characterized in that, The Ar group is an aromatic or heteroaromatic group with 12 to 30 cyclic carbon atoms.

3. The solar cell as described in claim 1 or 2, characterized in that, The Ar group includes at least one of the following Ar1 to Ar9 groups, and the dashed lines indicate the connection sites where the Ar group is used to directly or indirectly connect to a hydrogen group, the first group, or the second group: Y 1 Each group independently includes -CR 1 2-、-NR 1 -, -O-, -S-, -C(=O)-, -C(=CR 1 2) - one or more of them; R 1 Each group independently includes hydrogen groups, halogen groups, and R groups. 1 'R groups, halogen-substituted R 1 'group, -OR 1 '、-OCOR 1 '、-NR 1 '2、-SR 1 One or more of the following; R 1 Each group independently includes one or more of the following: substituted or unsubstituted phenyl, thiophene, and alkyl groups having 1 to 10 carbon atoms; n is greater than or equal to 1.

4. The solar cell according to any one of claims 1 to 3, characterized in that, The first group or the second group is independently connected to the Ar group via m L groups, where m ranges from 1 to 10, and each L group independently includes -CR 2 2-、-NR 2 -、-O-、-SiR 2 2-、-PR 2 -, -S-, -C(=O)-, -C(=S)-, -C(=NR 2 )-、-C(=CR 2 2) - or one or more of L1 to L8 below, where the dashed lines indicate the connection sites where the L group is used to connect the Ar group and to connect the first group or the second group; Y 2 Each group independently includes -CR 2 2-、-NR 2 -, -O-, -S-, -C(=O)-, -C(=CR 2 2) - one or more of them; R 2 Each group independently includes hydrogen groups, halogen groups, and R groups. 2 'R groups, halogen-substituted R 2 'group, -OR 2 '、-OCOR 2 '、-NR 2 '2、-SR 2 One or more of the following; R 2 Each group independently includes one or more of the following: substituted or unsubstituted phenyl, thiophene, and alkyl groups having 1-10 carbon atoms; Each Z group independently includes -CR 2 =, -N= or one or more of them.

5. The solar cell as described in claim 4, characterized in that, The L group independently includes -CR 2 2-、-NR 2 -, -O-, -C(=O)- or one or more of the following L9~L11:

6. The solar cell according to any one of claims 1 to 5, characterized in that, The structural formula of the functional material includes at least two first groups.

7. The solar cell according to any one of claims 1 to 6, characterized in that, The structural formula of the functional material includes at least two second groups.

8. The solar cell according to any one of claims 1 to 7, characterized in that, The cations of the salts corresponding to the carboxyl group and the salts corresponding to the phosphonic acid group include one or more of alkali metal cations, ammonium ions, and organic ammonium cations.

9. The solar cell according to any one of claims 1 to 8, characterized in that, Each of the organic ammonium cations independently comprises a substituted or unsubstituted C1-C20 alkylammonium cation, wherein, if the C1-C20 alkylammonium cation is substituted, the substituents independently comprise one or more of a hydroxyl group, a halogen, or a benzene ring; and / or each of the alkali metal cations independently comprises a sodium ion (Na+). + ), potassium ions (K) + ), rubidium ions (Rb + ) and cesium ions (Cs + One or more of them.

10. The solar cell according to any one of claims 1 to 9, characterized in that, The functional materials include one or more of the following SAM1 to SAM8:

11. The solar cell according to any one of claims 1 to 10, characterized in that, The thickness of the functional layer is 0.1 nm to 5 nm.

12. The solar cell according to any one of claims 1 to 11, characterized in that, The metal oxide layer is the first electrode layer or hole transport layer of the solar cell.

13. The solar cell according to claim 12, characterized in that, The first electrode layer comprises one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and indium zinc oxide (IZO); and / or the hole transport layer comprises one or more of nickel oxide, molybdenum oxide, and tungsten oxide.

14. The solar cell according to any one of claims 1 to 13, characterized in that, The solar cell is an inverted perovskite solar cell, which includes a first electrode layer, the functional layer, the light absorption layer, the electron transport layer, and the second electrode layer stacked sequentially, wherein the first electrode layer is the metal oxide layer; or, the inverted perovskite solar cell includes a first electrode layer, a hole transport layer, the functional layer, the light absorption layer, the electron transport layer, and the second electrode layer stacked sequentially, wherein the hole transport layer is the metal oxide layer.

15. The solar cell according to any one of claims 1 to 14, characterized in that, The light-absorbing layer comprises a perovskite material with the general formula ABX3 or A2CDX6, wherein A comprises inorganic, organic, or mixed organic-inorganic cations, including methylamine cations, ethylamine cations, propylamine cations, butylamine cations, pentamine cations, hexamine cations, formamidin cations, imidazole cations, and Cs. + 、Rb + Li + Na + K + Cu + Ag + Au + or Hg + One or more of the following; B includes inorganic cations, including Pb 2+ Sn 2+ One or more of the following; C includes inorganic or organic or mixed organic-inorganic cations, including Ag. + Cu + Au + FA + GA + D includes inorganic cations, including Bi. 3+ Sb 3+ Cr 3+ Fe 3+ Co 3+ Ga 3+ As 3+ Ru 3+ ,Rh 3+ In 3+ Ir 3+ Au 3+ Or Al 3+ One or more of them; X includes inorganic anions, including F - Cl - ,Br - I - SCN - CNO - OCN - OSCN - SH - OH - CN - SeCN - One or more of them.

16. A functional material, characterized in that, The functional material has a structural formula comprising an Ar group, at least one first group and at least one second group, wherein the first group and the second group are each independently directly or indirectly connected to the Ar group, the Ar group comprising a functional group having an aromatic ring, the first group comprising a carboxyl group or its corresponding salt, and the second group comprising a phosphonic acid group or its corresponding salt.

17. An electrical appliance, characterized in that, Including the solar cell as described in any one of claims 1 to 15.

18. A power generation device, characterized in that, Includes the solar cell as described in any one of claims 1 to 15.

19. A photovoltaic device, characterized in that, Including the solar cell as described in any one of claims 1 to 15.

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