Solar cell and manufacturing method thereof, solar cell module and manufacturing method thereof, and electric equipment

Abstract

The invention provides a solar cell and a manufacturing method thereof, a solar cell module and a manufacturing method thereof, and electric equipment. The solar cell comprises a first electrode layer, an active layer, a second electrode layer and a barrier layer which are sequentially stacked, the barrier layer is located between the active layer and the second electrode layer or located between the active layer and the first electrode layer, and the barrier layer comprises an n-type semiconductor oxide. The n-type semiconductor oxide is an inorganic material and has higher heat resistance compared with a traditional barrier layer material such as bath copper, so that the solar cell has higher heat stability by using the n-type semiconductor oxide as the barrier layer.

Description

Technical Field

[0001] The present application relates to the technical field of solar cell devices, and in particular to a solar cell and a manufacturing method thereof, a solar cell module and a manufacturing method thereof, and an electrical device. Background Art

[0002] With the large-scale development and utilization of non-renewable energy sources such as coal and oil, their storage capacity can no longer meet the development needs of various industries such as agriculture and industry. Therefore, recycled energy has gradually become one of the alternative energy sources to non-renewable energy sources to promote the development of society and industry. Among them, solar cell devices are widely used because of their green and environmentally friendly characteristics and the ability to output electrical energy when exposed to sunlight.

[0003] However, in the related art, the heat resistance of solar cell devices is poor, resulting in a short service life, which limits their further promotion and application. Summary of the invention

[0004] The present application provides a solar cell and a manufacturing method thereof, a solar cell module and a manufacturing method thereof, and an electrical device. The solar cell and the module have high thermal stability.

[0005] In a first aspect, an embodiment of the present application provides a solar cell, comprising: a first electrode layer, an active layer, a second electrode layer, and a barrier layer stacked in sequence, wherein the barrier layer is located between the active layer and the second electrode layer or between the active layer and the first electrode layer, and the barrier layer comprises an n-type semiconductor oxide.

[0006] N-type semiconductor oxide is an inorganic material and has higher heat resistance than traditional barrier layer materials such as bathocuproin. Therefore, using it as a barrier layer makes the solar cell have higher thermal stability.

[0007] In any embodiment, the hole mobility of the n-type semiconductor oxide is no more than 1000 cm 2 V -1 s -1 , optional 0.1cm 2 V -1 s -1 -1000cm 2 V -1 s -1 .

[0008] N-type semiconductor oxides have low hole mobility, which can effectively reduce the migration speed of holes, thereby blocking holes, reducing carrier recombination, and improving photoelectric conversion efficiency.

[0009] In any embodiment, the n-type semiconductor oxide includes at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0010] In any embodiment, the n-type semiconductor oxide comprises tin oxide.

[0011] Tin oxide also has a high electron mobility, which can not only block the diffusion of holes to the cathode, but also promote the transmission of electrons to the cathode. Therefore, it is beneficial to further improve the photoelectric conversion efficiency of solar cells.

[0012] In any embodiment, the thickness of the barrier layer is 5 nm-35 nm, and can be optionally 10 nm-30 nm.

[0013] When the thickness of the barrier layer is within a suitable range, the thermal stability and the photoelectric conversion efficiency of the solar cell can be improved simultaneously.

[0014] In any embodiment, the barrier layer is disposed between the second electrode layer and the active layer.

[0015] There is an electric field in the active layer (such as perovskite compounds), and halogen anions are prone to diffuse under the action of the electric field. Halogen anions have a low diffusion rate in n-type semiconductors. Using n-type semiconductor oxides as a barrier layer can also act as a passivation layer, effectively blocking the diffusion of halogen anions in the perovskite compound to the second electrode layer, slowing down the corrosion of the second electrode layer (such as a metal electrode), and improving the stability and photoelectric conversion efficiency of solar cells.

[0016] In any embodiment, the barrier layer further includes an extension portion disposed on at least one side of the active layer.

[0017] The extension portion arranged on at least one side of the active layer can form a semi-encapsulation structure for the solar cell, effectively blocking water and oxygen in the air from entering the active layer, especially blocking the aging of the light-absorbing layer in the active layer by water and oxygen, slowing down the degradation of the perovskite material in the external environment, and improving the photoelectric conversion efficiency and stability of the device.

[0018] In any embodiment, the portions of the barrier layer are formed simultaneously.

[0019] The various parts of the barrier layer are formed simultaneously during the deposition process, which can effectively improve the forming efficiency of the solar cell and reduce the deterioration of the photoelectric conversion efficiency caused by the damage to the active layer caused by multiple successive depositions.

[0020] In any embodiment, the barrier layer is prepared by atomic layer deposition.

[0021] The thin film prepared by atomic layer deposition has high density and can effectively block the diffusion of halogen anions in the active layer to the second electrode layer. In particular, it can alleviate the corrosion of halogen anions on the metal in the electrode layer, effectively improving the stability and photoelectric conversion efficiency of solar cells. At the same time, the atomic layer deposition method is to alternately pass the gas phase precursor pulses into the reaction vessel. The first reaction precursor will chemically adsorb on the substrate. When the second precursor is passed into the reaction vessel, it will react with the previous precursor that has been adsorbed on the surface of the substrate to form a thin film. Therefore, the film formation of the atomic layer deposition method is not restricted by direction and angle. The reaction precursor can be freely adsorbed on any exposed surface of the active layer, so that the barrier layer can be formed simultaneously in all directions, which has the characteristics of high production efficiency and low cost.

[0022] Moreover, the film layer prepared by atomic layer deposition is dense and has a low ion diffusion rate. Compared with other deposition methods, it can more effectively block the migration of halogen ions in the active layer to the electrode layer, slow down the corrosion of halogen ions on the electrode layer, especially on the metal electrode, and thus improve the photoelectric conversion efficiency and device stability of solar cells.

[0023] In any embodiment, the active layer comprises a light absorbing layer, and optionally, the light absorbing layer comprises a perovskite compound.

[0024] In any embodiment, the active layer further includes an electron transport layer, and the electron transport layer is disposed between the light absorbing layer and the blocking layer.

[0025] Compared with directly setting the blocking layer on the surface of the light absorbing layer, the blocking layer is arranged on the surface of the electron transport layer, which can effectively reduce the damage to the light absorbing layer during the deposition of the blocking layer and reduce the negative impact on the photoelectric conversion efficiency.

[0026] In any embodiment, the active layer further includes a hole transport layer, and the hole transport layer is disposed on a side of the light absorbing layer away from the blocking layer.

[0027] In any embodiment, the highest occupied molecular orbital (HOMO) energy level of the n-type semiconductor oxide is lower than the highest occupied molecular orbital (HOMO) energy level of the light absorbing layer.

[0028] The highest occupied molecular orbital of the n-type semiconductor oxide is lower than the highest occupied molecular orbital energy level of the electron transport layer and / or the light absorbing layer, and can block holes from diffusing from the highest occupied molecular orbital of the light absorbing layer to the highest occupied molecular orbital of the n-type semiconductor oxide, thereby acting as a hole blocking layer.

[0029] The second aspect of the present application provides a method for preparing a solar cell, the preparation method comprising: providing a first electrode layer; forming an active layer on at least one side of the first electrode layer; forming a barrier layer on a side of the active layer away from the first electrode layer; forming a second electrode layer on a side of the barrier layer away from the first electrode layer; the barrier layer comprises an n-type semiconductor oxide, optionally comprising at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0030] In any embodiment, the barrier layer further includes an extension portion disposed on at least one side of the active layer.

[0031] In any embodiment, the barrier layer is formed by atomic layer deposition.

[0032] The third aspect of the present application provides a solar cell module, comprising a first electrode layer, an active layer, a barrier layer, and a second electrode layer stacked in sequence, wherein the barrier layer comprises an n-type semiconductor oxide, optionally comprising at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0033] Using n-type semiconductor oxide as a barrier layer can play a role in blocking the migration of holes toward the cathode. N-type semiconductor oxide is an inorganic material and has higher heat resistance than traditional barrier layer materials such as bathocuproin, making the solar cell module have higher thermal stability.

[0034] In any embodiment, the first electrode layer includes a plurality of conductive blocks that are not interconnected, and a first separation groove is arranged between adjacent conductive blocks; the active layer includes a plurality of active blocks, and a second separation groove is arranged between adjacent active blocks, the bottom surface of the second separation groove is arranged on the first electrode layer, and the opening of the second separation groove is arranged on the upper surface of the active layer; the second electrode layer is arranged on the barrier layer, and the second electrode layer also has a longitudinal portion extending toward the first electrode layer, the longitudinal portion passes through the second separation groove, and the end of the longitudinal portion is connected to the bottom surface of the second separation groove; the solar cell assembly also includes a third separation groove, the opening of the third separation groove is arranged on the upper surface of the second electrode layer, and the bottom surface of the third separation groove is arranged on the first electrode layer.

[0035] The above arrangement enables solar cell monomers to be connected in series to form a solar cell module through a simple separation groove arrangement, thereby effectively improving the preparation efficiency of the solar cell module.

[0036] In any embodiment, the barrier layer at least includes a first horizontal portion located on the upper surface of the active block and a first extending portion extending toward the first electrode, and the first extending portion is disposed on at least one side of the active layer adjacent to the second separation groove.

[0037] The first horizontal portion and the first extension portion of the barrier layer can respectively inhibit the longitudinal migration and lateral migration of halogen anions in the active layer to the second electrode layer, slow down the corrosion of the second electrode layer, and improve the stability and photoelectric conversion efficiency of the solar cell module.

[0038] In any embodiment, the blocking layer also includes a second horizontal portion located at the bottom surface of the second separation groove; a fourth separation groove is provided on the second horizontal portion, and the longitudinal portion of the second electrode layer passes through the fourth separation groove so that its end is connected to the first electrode layer on the bottom surface of the second separation groove.

[0039] The longitudinal portion of the second electrode layer passes through the fourth separation groove so that its end is connected to the first electrode layer at the bottom of the second separation groove, which can reduce the series resistance between solar cell monomers and improve the photoelectric conversion efficiency of the solar cell module.

[0040] In any embodiment, the width of the fourth separation groove is smaller than the width of the second separation groove.

[0041] The above arrangement enables the end of the longitudinal portion of the second electrode layer to be connected to the first electrode layer at the bottom of the second separation groove, and the arrangement of the fourth separation groove will not destroy the first extension portion of the barrier layer, so that it can play an effective barrier role and will not have other negative effects on the photoelectric conversion efficiency and stability of the solar cell module.

[0042] In any embodiment, the barrier layer is prepared by atomic layer deposition. Optionally, the barrier layer has a thickness of 5 nm-35 nm, and optionally 10 nm-30 nm.

[0043] In any embodiment, the active layer includes a light absorbing layer, optionally, the light absorbing layer includes a perovskite compound, optionally, the active layer also includes an electron transport layer, and the electron transport layer is arranged between the light absorbing layer and the blocking layer; optionally, the active layer also includes a hole transport layer, and the hole transport layer is arranged between the battery light absorbing layer and the first electrode layer.

[0044] The fourth aspect of the present application provides a method for preparing a solar cell assembly, the method comprising: providing a first electrode layer; forming at least one first separation groove on the first electrode layer, the first separation groove dividing the first electrode layer into a plurality of mutually unconnected conductive blocks; forming an active layer on at least one side of the first electrode layer; forming at least one second separation groove on the active layer, the bottom surface of the second separation groove being arranged on the first electrode layer, and the opening of the second separation groove being arranged on the upper surface of the active layer; forming a barrier layer on the side of the active layer away from the first electrode layer; forming a second electrode layer on the side of the barrier layer away from the first electrode layer; the second electrode layer having a longitudinal portion extending toward the first electrode layer, the longitudinal portion filling the second separation groove, and the end of the longitudinal portion being connected to the first electrode layer at the bottom of the second separation groove; forming a third separation groove, the opening of the third separation groove being arranged on the upper surface of the second electrode layer, and the bottom surface of the third separation groove being arranged on the first electrode layer; the barrier layer comprises an n-type semiconductor oxide, optionally comprising at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0045] In any embodiment, the barrier layer is formed at least on the upper surface of the active block and at least one side surface of the active block adjacent to the second separation groove.

[0046] In any embodiment, the barrier layer is prepared by atomic layer deposition.

[0047] In any embodiment, the blocking layer is also formed on the bottom surface of the second separation groove; a fourth separation groove is formed on the blocking layer located on the bottom surface of the second separation groove, the longitudinal portion of the second electrode layer passes through the fourth separation groove, and the end of the longitudinal portion is connected to the first electrode layer on the bottom surface of the second separation groove.

[0048] The fifth aspect of the present application provides an electrical device, including the solar cell of the first aspect of the present application or the solar cell prepared by the preparation method of the second aspect of the present application or the solar cell module of the third aspect of the present application or the solar cell module prepared by the preparation method of the fourth aspect of the present application.

[0049] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present application. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0051] Figure 1 A schematic diagram of a cross-sectional structure of a solar cell provided in some embodiments of the present application is shown;

[0052] Figure 2 A schematic diagram of a cross-sectional structure of a solar cell provided in some embodiments of the present application is shown;

[0053] Figure 3 A schematic diagram of a cross-sectional structure of a solar cell provided in some embodiments of the present application is shown;

[0054] Figure 4 A schematic diagram of a cross-sectional structure of a solar cell provided in some embodiments of the present application is shown;

[0055] Figure 5 A schematic diagram of a cross-sectional structure of a solar cell provided in some embodiments of the present application is shown;

[0056] Figure 6 A schematic diagram of energy levels of solar cells provided in some embodiments of the present application is shown;

[0057] Figure 7 A schematic cross-sectional structure diagram of a solar cell assembly provided in some embodiments of the present application is shown;

[0058] Figure 8 The I in the second electrode layer of the solar cell module after aging in Example 1 and Comparative Example 1 of the present application is shown. 3d X-ray photoelectron spectroscopy (XPS) spectrum.

[0059] The reference numerals in the specific implementation manner are as follows:

[0060] Solar cells 1-1, 1-2, 1-3, 1-4, 1-5;

[0061] Solar cell module 2;

[0062] First electrode layers 10, 20;

[0063] Active layers 11, 21, light absorbing layer 111, electron transport layer 112, hole transport layer 113

[0064] The second electrode layer 12, 22; the longitudinal portion 221;

[0065] Barrier layers 13, 23; extension portion 131; first horizontal portion 232; first extension portion 231; second horizontal portion 233

[0066] The first separation tank P-1; the second separation tank P-2; the third separation tank P-3; the fourth separation tank P-4. DETAILED DESCRIPTION

[0067] The following embodiments of the technical solution of the present application are described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0068] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.

[0069] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.

[0070] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0071] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0072] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).

[0073] In the description of the embodiments of the present application, the orientations or positional relationships indicated by technical terms such as "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", and "circumferential" are based on the orientations or positional relationships shown in the accompanying drawings and are only for the convenience of describing the embodiments of the present application and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the embodiments of the present application.

[0074] In the description of the embodiments of the present application, unless otherwise clearly specified and limited, technical terms such as "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, and it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the embodiments of the present application can be understood according to the specific circumstances.

[0075] 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproin, BCP) is a commonly used barrier layer material in solar cells (especially perovskite solar cells). It improves the photoelectric conversion efficiency of solar cells by blocking the migration of holes toward the cathode. However, bathocuproin is an organic substance that easily aggregates under heat, resulting in poor thermal stability of solar cells.

[0076] Based on this, Figure 1 and Figure 2 As shown, the first aspect of the present application provides a solar cell 1-1, 1-2, which includes: a first electrode layer 10, an active layer 11, a second electrode layer 12, and a blocking layer 13 stacked in sequence, the blocking layer 13 is located between the active layer 11 and the second electrode layer 12 or between the active layer 11 and the first electrode layer 10, and the blocking layer 13 includes an n-type semiconductor oxide.

[0077] N-type semiconductor oxide is also called electronic semiconductor oxide, that is, an impurity semiconductor oxide in which the free electron concentration is much greater than the hole concentration.

[0078] In some embodiments, the blocking layer is a hole blocking layer.

[0079] N-type semiconductor oxide is an inorganic material and has higher heat resistance than traditional barrier layer materials such as bathocuproin. Therefore, using it as a barrier layer makes the battery have higher thermal stability.

[0080] In some embodiments, the hole mobility of the n-type semiconductor oxide is no more than 1000 cm 2 V -1 s -1 , optional 0.1cm 2 V -1 s -1 -1000cm 2 V -1 s -1 .

[0081] Hole mobility refers to the rate at which holes move under the action of an electric field.

[0082] In some embodiments, the hole mobility of the n-type semiconductor oxide may be 0.1 cm 2 V -1 s -1 , 1cm 2 V -1 s -1 , 10cm 2 V -1 s -1 , 100cm 2 V -1 s -1 , 500cm 2 V -1 s -1 , 1000cm 2 V -1 s -1 or any value in between.

[0083] N-type semiconductor oxides have low hole mobility, which can effectively reduce the migration speed of holes, thereby blocking holes, reducing carrier recombination, and improving photoelectric conversion efficiency.

[0084] In some embodiments, the n-type semiconductor oxide includes at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide. In some embodiments, the n-type semiconductor oxide includes tin oxide.

[0085] Tin oxide also has a high electron mobility, which can not only block the diffusion of holes to the cathode, but also promote the transmission of electrons to the cathode. Therefore, it is beneficial to further improve the photoelectric conversion efficiency of solar cells.

[0086] In some embodiments, the thickness of the barrier layer 13 is 5 nm to 35 nm, and may be 10 nm to 30 nm.

[0087] When the thickness of the barrier layer is within a suitable range, the thermal stability and the photoelectric conversion efficiency of the solar cell can be improved simultaneously.

[0088] In some embodiments, the solar cells 1-1 and 1-2 may include perovskite cells, fuel cell-sensitized solar cells, etc. Optionally, the solar cell includes a perovskite cell.

[0089] In some embodiments, Figure 3 and Figure 4 As shown, the active layer 11 includes a light absorbing layer 111 . Optionally, the light absorbing layer 111 includes a perovskite compound.

[0090] In some embodiments, the thickness of the light absorbing layer 111 is 400 nm to 1000 nm. For example, the thickness of the light absorbing layer can be 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or within a range of any of the above values. Optionally, the thickness of the light absorbing layer 111 is 500 nm to 900 nm.

[0091] In some embodiments, the band gap of the perovskite compound is 1.20 eV to 2.30 eV. For example, the band gap of the perovskite compound can be 1.20 eV, 1.50 eV, 2.00 eV, 2.30 eV, or any range thereof.

[0092] In some embodiments, the perovskite compound comprises a perovskite-type metal halide; the chemical formula of the perovskite-type metal halide is ABX 3 ; wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion. In some embodiments, A includes Cs + , K + , Rb + , one or more of a monovalent amine cation and a monovalent amidine cation. Non-limiting examples of monovalent amine cations include CH 3 NH 3 + (Methylamine, MA + ), ammonium (NH 4 + ). Non-limiting examples of monovalent amidinium cations include NH 2 CH=NH 2 + (Formamidine, can be written as FA + ). In some embodiments, B includes Pb 2+ Sn 2+ , Fe 2+ , Mn 2+ 、Ni 2+ ,Ge 2+ 、Co 2 + and Sb 2+In some embodiments, X comprises a halogen anion. In some embodiments, X comprises Cl - Br - ,I - At least one of .

[0093] In some embodiments, Figure 3 and Figure 4 As shown, the active layer 11 further includes an electron transport layer 112 , and the electron transport layer 112 is disposed between the light absorbing layer 111 and the blocking layer 13 .

[0094] In some embodiments, the electron transport layer 112 includes at least one of the following materials and their derivatives: [6,6]-phenyl-C61-butyric acid isomethyl ester (PC 61 BM), [6,6]-phenyl C71 butyric acid methyl ester (PC 71 BM), fullerene.

[0095] The blocking layer 13 is disposed on the surface of the electron transport layer 112 , which can effectively reduce the damage to the light absorbing layer 111 during the deposition of the blocking layer 13 and reduce the negative impact on the photoelectric conversion efficiency, compared with directly disposing the blocking layer 13 on the surface of the light absorbing layer 111 .

[0096] In some embodiments, Figure 3 and Figure 4 As shown, the active layer 11 further includes a hole transport layer 113 , and the hole transport layer 113 is disposed on a side of the light absorbing layer 111 away from the blocking layer 13 .

[0097] In some embodiments, the hole transport layer 113 includes at least one of the following materials and their derivatives: BTPA series hole transport materials, poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), 2,2',7,7'-tetrakis [N,N-di (4-methoxyphenyl) amino] -9,9'-spirobifluorene (Spiro-OMeTAD), poly-3-hexylthiophene (P 3 HT), triphenylamine with triptycene as the core (H 101 )、3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-anilino)carbazole-spirobifluorene (CzPAF-SBF), poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (Cu 2 O).

[0098] In some embodiments, the first electrode layer 10 is a transparent electrode layer, and the second electrode layer 12 is a back electrode layer.

[0099] In some embodiments, the first electrode layer 10 includes at least one of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), and indium tungsten oxide (IWO).

[0100] In some embodiments, the thickness of the first electrode layer 10 is 200 nm to 1000 nm. For example, the thickness of the transparent conductive layer can be 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm or any range thereof.

[0101] In some embodiments, the second electrode layer 12 is generally a metal electrode, an inorganic electrode or a metal-inorganic electrode mixed conductive material. In some embodiments, the back electrode layer 12 comprises at least one of indium tin oxide (ITO), lanthanide metal-doped indium oxide, boron-doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), indium tungsten oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and alloys thereof, graphite, graphene, and carbon nanotubes; optionally Ag, Cu, C, Au, Al, ITO, AZO, BZO or IZO, and further optionally Cu, Ag, Au or a combination thereof.

[0102] In some embodiments, the thickness of the second electrode layer 12 is 20 nm to 200 nm. For example, the thickness of the back electrode layer can be 20 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm or any range thereof.

[0103] In some embodiments, Figure 3 As shown, the solar cell 1-3 is an inverted pin perovskite cell, which includes a first electrode layer 10, a hole transport layer 113, a light absorption layer 111, an electron transport layer 112, a blocking layer 13, and a second electrode layer 12 stacked in sequence.

[0104] In some embodiments, Figure 4 As shown, the solar cell 1-4 is a formal nip perovskite cell, including a first electrode layer 10, a blocking layer 13, an electron transport layer 112, a light absorption layer 111, a hole transport layer 113, and a second electrode layer 12 stacked in sequence.

[0105] In some embodiments, Figure 3 As shown, the barrier layer 13 is disposed between the second electrode layer 12 and the active layer 11 .

[0106] There is an electric field in the active layer 11 (such as a perovskite compound), and halogen anions are easily diffused under the action of the electric field. Halogen anions have a low diffusion rate in n-type semiconductors. Using n-type semiconductor oxide as the barrier layer 13 can not only block holes, but also block the diffusion of halogen anions in the perovskite compound to the second electrode layer 12, slowing down the corrosion of the second electrode layer 12 (such as a metal electrode), and improving the stability and photoelectric conversion efficiency of solar cells.

[0107] In some embodiments, Figure 5 As shown, the barrier layer 13 further includes an extension portion 131 disposed on at least one side of the active layer 11 .

[0108] In some embodiments, the thickness of the extension portion 131 of the barrier layer 13 is 5 nm-35 nm, and may be 10 nm-30 nm.

[0109] The extension portion 131 arranged on at least one side of the active layer 11 can form a semi-encapsulation structure for the solar cell 1-5, effectively blocking water and oxygen in the air from entering the active layer 11, especially blocking the aging of the light-absorbing layer 111 by water and oxygen, slowing down the degradation of the perovskite material in the external environment, and improving the photoelectric conversion efficiency and stability of the device.

[0110] In some embodiments, portions of barrier layer 13 are formed simultaneously.

[0111] The various parts of the barrier layer 13 are formed simultaneously in one deposition process, which can effectively improve the forming efficiency of the solar cell and reduce the deterioration of the photoelectric conversion efficiency caused by the damage to the active layer 11 caused by multiple depositions.

[0112] In some embodiments, the barrier layer 13 is prepared by atomic layer deposition.

[0113] Atomic layer deposition is a method that can deposit materials layer by layer on the surface of a substrate in the form of a single atomic film.

[0114] The film prepared by the atomic layer deposition method has high compactness, can effectively block the diffusion of halogen anions in the light-absorbing layer 111 to the second electrode layer 12, and can especially alleviate the corrosion of halogen anions to the metal in the electrode layer, effectively improving the stability and photoelectric conversion efficiency of solar cells. At the same time, the atomic layer deposition method is to alternately pass the gas phase precursor pulses into the reaction vessel, the first reaction precursor will be chemically adsorbed on the substrate, and when the second precursor is passed into the reaction vessel, it will react with the previous precursor that has been adsorbed on the surface of the substrate to form a thin film. Therefore, the film formation of the atomic layer deposition method is not restricted by direction and angle, and the reaction precursor can be freely adsorbed on any exposed surface of the active layer, so that the blocking layer 13 can be formed simultaneously in all directions, which has the characteristics of high production efficiency and low cost.

[0115] In some embodiments, the highest occupied molecular orbital (HOMO) energy level of the n-type semiconductor oxide is lower than the highest occupied molecular orbital (HOMO) energy level of the light absorbing layer.

[0116] like Figure 6 As shown, the highest occupied molecular orbital of the n-type semiconductor oxide is lower than the highest occupied molecular orbital of the electron transport layer 112 and / or the light absorbing layer 111, which can block the diffusion of holes from the highest occupied molecular orbital of the light absorbing layer 111 to the highest occupied molecular orbital of the n-type semiconductor oxide, thus playing the role of a blocking layer.

[0117] In some embodiments, the n-type semiconductor oxide has a lowest unoccupied molecular orbital (LUMO) energy level of -6 eV to -4.3 eV, and a highest occupied molecular orbital (HOMO) energy level of -8 eV to -6.2 eV.

[0118] like Figure 6 As shown, the highest occupied molecular orbital of the n-type semiconductor oxide within the above range is lower than the highest occupied molecular orbital of the electron transport layer 112 and / or the light absorbing layer 111, which can block the diffusion of holes from the highest occupied molecular orbital of the light absorbing layer 111 to the highest occupied molecular orbital of the n-type semiconductor oxide, and plays the role of a hole blocking layer; at the same time, the lowest unoccupied molecular orbital of the n-type semiconductor oxide matches the lowest unoccupied molecular orbital of the electron transport layer 112 and / or the light absorbing layer 111, which is beneficial for the diffusion of electrons after transition from the lowest unoccupied molecular orbital of the light absorbing layer 111 and / or the electron transport layer 112 to the blocking layer 13, further improving the electron transmission efficiency, and facilitating the improvement of the photoelectric conversion efficiency of the solar cell.

[0119] The second aspect of the present application provides a method for preparing a solar cell. Please continue to refer to Figure 3The preparation method includes: providing a first electrode layer 10; forming an active layer 11 on at least one side of the first electrode layer 10; forming a barrier layer 13 on the side of the active layer 11 away from the first electrode layer 10; forming a second electrode layer 12 on the side of the barrier layer 13 away from the first electrode layer 10; the barrier layer includes an n-type semiconductor oxide, optionally including at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0120] In some embodiments, the barrier layer 13 further includes an extension portion 131 disposed on at least one side of the active layer 11 .

[0121] In some embodiments, the barrier layer 13 is formed by atomic layer deposition.

[0122] In some embodiments, the barrier layer 13 is formed by atomic layer deposition using a metal source and an oxygen source.

[0123] In some embodiments, the metal source includes at least one of an organic tin source, an organic titanium source, and an organic zinc source.

[0124] In some embodiments, the tin source comprises an organotin source, optionally tetrakis(dimethylamino)tin.

[0125] In some embodiments, the oxygen source includes at least one of water and ozone.

[0126] The third aspect of this application is as follows: Figure 6 As shown, a solar cell assembly 2 is provided, comprising a first electrode layer 20, an active layer 21, a barrier layer 23, and a second electrode layer 22 stacked in sequence, wherein the barrier layer 23 comprises an n-type semiconductor oxide, optionally comprising at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0127] A solar cell module is formed by connecting several solar cell monomers in series or in parallel. Using n-type semiconductor oxide as a barrier layer can block the migration of holes toward the cathode. n-type semiconductor oxide is an inorganic material and has higher heat resistance than traditional barrier layer materials such as bathocuproin, making the solar cell module have higher thermal stability.

[0128] In some embodiments, continue to refer to Figure 6The first electrode layer 20 includes a plurality of conductive blocks that are not interconnected, and a first separation groove P-1 is arranged between adjacent conductive blocks; the active layer 21 includes a plurality of active blocks, and a second separation groove P-2 is arranged between adjacent active blocks, the bottom surface of the second separation groove P-2 is arranged on the first electrode layer 20, and the opening of the second separation groove P-2 is arranged on the upper surface of the active layer 21; the second electrode layer 22 is arranged on the barrier layer 23, and the second electrode layer 22 also has a longitudinal portion 221 extending toward the first electrode layer 20, the longitudinal portion 221 passes through the second separation groove P-2, and the end of the longitudinal portion 221 is connected to the bottom surface of the second separation groove P-2; the solar cell assembly 2 also includes a third separation groove P-3, the opening of the third separation groove P-3 is arranged on the upper surface of the second electrode layer 22, and the bottom surface of the third separation groove P-3 is arranged on the first electrode layer 20.

[0129] The above arrangement enables solar cell monomers to be connected in series to form a solar cell module through a simple separation groove arrangement, thereby effectively improving the preparation efficiency of the solar cell module.

[0130] In some embodiments, the barrier layer 23 includes at least a first horizontal portion 232 located on the upper surface of the active block and a first extension portion 231 extending toward the first electrode 20 , and the first extension portion 231 is disposed on at least one side of the active layer 21 adjacent to the second separation groove P- 2 .

[0131] The first horizontal portion 232 and the first extension portion 231 of the barrier layer 23 can respectively inhibit the longitudinal and lateral migration of halogen anions in the active layer 21 to the second electrode layer 22, slowing down the corrosion of the second electrode layer 22 and improving the stability and photoelectric conversion efficiency of the solar cell module.

[0132] In some embodiments, the blocking layer 23 also includes a second horizontal portion 233 located at the bottom surface of the second separation groove P-2; a fourth separation groove P-4 is provided on the second horizontal portion 233, and the second electrode layer longitudinal portion 221 passes through the fourth separation groove P-4 so that its end is connected to the first electrode layer 20 of the bottom surface P-2 of the second separation groove.

[0133] The second electrode layer longitudinal portion 221 passes through the fourth separation groove P-4 so that its end is connected to the first electrode layer 20 at the bottom of the second separation groove P-2, which can reduce the series resistance between solar cell monomers and improve the photoelectric conversion efficiency of the solar cell module.

[0134] In some embodiments, the width of the fourth separation groove P-4 is smaller than the width of the second separation groove P-2.

[0135] The above-mentioned arrangement enables the end of the longitudinal portion 221 of the second electrode layer to be connected to the first electrode layer 20 at the bottom surface of the second separation groove P-2, and the arrangement of the fourth separation groove P-4 will not destroy the first extension portion 231 of the blocking layer 23, so that it can play an effective barrier role and will not have other negative effects on the photoelectric conversion efficiency and stability of the solar cell module.

[0136] In some embodiments, barrier layer 23 is prepared by atomic layer deposition.

[0137] Atomic layer deposition is a method that can coat a substance layer by layer on the surface of a substrate in the form of a single atomic film. Therefore, the film deposited by the atomic layer deposition method has high density, can effectively block the diffusion of halogen anions in the active layer 21 to the second electrode layer 22, and can especially alleviate the corrosion of halogen anions to the metal in the electrode layer, effectively improving the stability and photoelectric conversion efficiency of solar cells. At the same time, the atomic layer deposition method is to alternately pass the gas phase precursor pulse into the reaction vessel, the first reaction precursor will chemically adsorb on the substrate, and when the second precursor is passed into the reaction vessel, it will react with the previous precursor that has been adsorbed on the surface of the substrate to form a thin film. Therefore, the film formation of the atomic layer deposition method is not restricted by direction and angle, and the reaction precursor can be freely adsorbed on any side exposed by the active layer, so as to realize the simultaneous molding of the first extension portion 231, the first horizontal portion 232 and the second horizontal portion 233 of the barrier layer, and has the characteristics of high production efficiency and low cost.

[0138] In some embodiments, the thickness of the barrier layer 23 is 5 nm to 35 nm, and may be 10 nm to 30 nm.

[0139] In some embodiments, the first horizontal portion 232 , the first extension portion 231 , and the second horizontal portion 233 of the barrier layer 23 have the same thickness.

[0140] In some embodiments, the active layer 21 includes a light absorbing layer.

[0141] In some embodiments, the light absorbing layer 211 includes a perovskite compound;

[0142] In some embodiments, the active layer 21 further includes an electron transport layer 212 , and the electron transport layer 212 is disposed between the light absorbing layer 211 and the blocking layer 23 .

[0143] In some embodiments, the active layer 21 further includes a hole transport layer 213 , and the hole transport layer 213 is disposed between the light absorbing layer 211 and the first electrode layer 20 .

[0144] A fourth aspect of the present application provides a method for preparing a solar cell assembly 2, providing a first electrode layer 20; forming at least one first separation groove P-1 on the first electrode layer 20, the first separation groove P-1 dividing the first electrode layer 20 into a plurality of mutually unconnected conductive blocks; forming an active layer 21 on at least one side of the first electrode layer 20; forming at least one second separation groove P-2 on the active layer 21, the bottom surface of the second separation groove P-2 being arranged on the first electrode layer 20, and the opening of the second separation groove P-2 being arranged on the upper surface of the active layer 21; forming a barrier layer 23 on the side of the active layer 21 away from the first electrode layer 20; and forming a barrier layer 23 on the barrier layer 21. A second electrode layer 22 is formed on the side of the blocking layer 23 facing away from the first electrode layer 20; the second electrode layer 22 has a longitudinal portion 221 extending toward the first electrode layer 20, the longitudinal portion 221 fills the second separation groove P-2, and the end of the longitudinal portion 221 is connected to the first electrode layer 20 at the bottom of the second separation groove P-2; a third separation groove P-3 is formed, the opening of the third separation groove P-3 is arranged on the upper surface of the second electrode layer 22, and the bottom surface of the third separation groove P-3 is arranged on the first electrode layer 20; the blocking layer includes an n-type semiconductor oxide, optionally, including at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0145] Different from the prior art, the second separation groove P-2 is formed before the barrier layer 23 is deposited, so that the barrier layer 23 can be deposited simultaneously on the upper surface of the active block and at least one side of the active block adjacent to the second separation groove P-2, thereby improving the production efficiency while improving the photoelectric conversion efficiency and stability of the solar cell module.

[0146] In some embodiments, the barrier layer 23 is formed at least on the upper surface of the active block and at least one side surface of the active block adjacent to the second separation trench P-2.

[0147] In some embodiments, barrier layer 23 is prepared by atomic layer deposition.

[0148] In some embodiments, the blocking layer 23 is also formed on the bottom surface of the second separation groove P-2; a fourth separation groove P-4 is formed on the blocking layer 23 located on the bottom surface of the second separation groove P-2, and the longitudinal portion 221 of the second electrode layer passes through the fourth separation groove P-4, and the end of the longitudinal portion 221 is connected to the first electrode layer 20 on the bottom surface of the second separation groove P-2.

[0149] In some embodiments, at least one of the first separation groove P-1, the second separation groove P-2, the third separation groove P-3, and the fourth separation groove P-4 is formed by laser cutting.

[0150] Laser cutting is precise and efficient, and can effectively improve the processing accuracy of solar cell modules and reduce manufacturing costs.

[0151] The fifth aspect of the present application provides an electrical device, including a solar cell in any embodiment or a solar cell prepared by a preparation method in any embodiment or a solar cell module in any embodiment or a solar cell module prepared by a preparation method in any embodiment.

[0152] In some embodiments, the solar cell or solar cell module can be used as a power generation device for an electrical device. The type of power generation device may include but is not limited to integrated power generation.

[0153] The electrical devices may include mobile devices such as mobile phones, tablet computers, laptop computers, calculators, watches, cars, electric trains, ships and satellites, power generation systems, etc., but are not limited thereto.

[0154] The location of the power generation device may include but is not limited to the roof, back panel, etc. of the car.

[0155] The following examples more specifically describe the disclosure of the present application, which are intended for illustrative purposes only, as it will be apparent to those skilled in the art that various modifications and variations may be made within the scope of the disclosure of the present application. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further processing, and the instruments used in the examples are commercially available.

[0156] Example

[0157] Preparation method

[0158] Example 1

[0159] The present invention provides a method for manufacturing a solar cell module, which comprises the following steps:

[0160] Preparation of the first electrode layer: ultrasonically clean the etched FTO conductive glass several times with water, acetone, and isopropanol, and then blow dry with nitrogen for later use as the first electrode layer;

[0161] Using a laser to draw a first separation groove (P1) on the cleaned FTO substrate, etching away the FTO conductive layer to expose the substrate;

[0162] Preparation of the hole transport layer: The transparent conductive glass substrate was treated with UV ozone, and then nickel oxide with a thickness of about 30 nm was magnetron sputtered, and annealed at 300°C for 60 minutes to obtain the hole transport layer;

[0163] Preparation of perovskite layer: The perovskite light absorption layer was prepared by a one-step method. The perovskite precursor solution was spin-coated on the hole transport layer at a speed of 3000-5000 rpm for 20-40 seconds. 300-600 uL of anti-solvent was added at about 10 seconds after the start of spin coating. The film was then placed on a hot plate and annealed at 100-120°C for 60 minutes to obtain a perovskite layer with a thickness of 600 nm.

[0164] The perovskite precursor solution was prepared by dissolving 116.91 mg of cesium iodide, 94.19 mg of methylamine chloride, 1440.94 mg of formamidine iodine, 4356.54 mg of lead iodide, 66.06 mg of lead bromide, and 111.97 mg of methylamine bromide in 6 mL of a mixed solvent of DMF and DMSO, wherein the volume ratio of DMF to DMSO was 4:1, and the anti-solvent was anisole;

[0165] Preparation of electron transport layer: Place the film with perovskite layer into the evaporator and wait until the vacuum degree of evaporation reaches 5×10 -4 Pa below, evaporate 20nm electron transport layer C at a rate of 0.05A / s 60 ;

[0166] A second separation groove with a width of 50 μm is manufactured on the electron transport layer by using a laser, and the hole transport layer, the light absorption layer and the electron transport layer are etched away to expose the first electrode layer;

[0167] A layer of tin dioxide with a thickness of about 25 nm is prepared as a barrier layer on a substrate with a second separation groove by atomic layer deposition technology; the barrier layer is deposited on any exposed surface on the substrate with the second separation groove, including the upper surface and side surfaces of the active block and the bottom surface of the second separation groove; the specific deposition process is as follows: the tin source used is tetrakis(dimethylamino)tin (TDMASn), the oxygen source used is water, the pulse and purge time is TDMASn 0.5s, nitrogen 3s, water 0.5s, nitrogen 5s, the local pressure is 50mtorr, the flushing flow rate is 5000sccm, the reaction temperature is 100°C, and the source temperature is 45°C.

[0168] The barrier layer on the bottom surface of the second separation groove is etched away by laser scribing at the middle position of the bottom of the second separation groove to manufacture a fourth separation groove with a width of 30 μm, so as to expose the first electrode layer below without damaging the tin dioxide on the side surface of the second separation groove;

[0169] The film with barrier layer was placed in the evaporation apparatus and the vacuum degree of evaporation was increased to 5×10 -4 Pa, evaporating 80nm of metal electrode Cu at a rate of 0.1A / s as the second electrode layer, and the metal copper simultaneously fills the second separation groove and is connected with the first electrode layer exposed at the bottom of the second separation groove;

[0170] A third separation groove is manufactured on the second electrode layer by using laser, and all functional layer films on the first electrode layer are etched away to obtain a solar cell module.

[0171] The preparation method of Example 2-3 is basically the same as that of Example 1, except that the composition of the barrier layer is changed; in the atomic layer deposition process of Example 2, Ti(NMe 2 ) 4 is a titanium source, water is an oxygen source, the barrier layer includes titanium dioxide, and ZnMe 2 is the zinc source, water is the oxygen source, and the barrier layer comprises zinc oxide.

[0172] In Example 4, fluorine-doped tin dioxide was used as a target material, and a 25 nm thick impedance layer was prepared by magnetron sputtering deposition.

[0173] The preparation methods of Examples 5-8 are substantially the same as those of Example 1, except that the thickness of the barrier layer is changed by adjusting the deposition time of the barrier layer;

[0174] The preparation method of Example 9 is substantially the same as that of Example 1, except that the side of the active layer is shielded during the atomic layer deposition process, so that the barrier layer is only atomically deposited on the surface of the active layer and not on the side thereof;

[0175] The preparation method of Example 10 is substantially the same as that of Example 1, except that the fourth separation groove is not provided, and the second electrode cannot directly contact the first electrode;

[0176] The preparation method of Example 11 is basically the same as that of Example 1, except that the barrier layer tin dioxide is prepared by deposition using tin dioxide as a target material through a magnetron sputtering method.

[0177] The steps of Comparative Example 1 are basically the same as those of Example 1, except that the component of the barrier layer in Comparative Example 1 is bathocuproin (BCP), and the deposition method of the barrier layer is:

[0178] The BCP barrier layer was prepared by spin coating with a concentration of 5 mg / mL, the solvent being isopropanol, the spin coating speed being 4000 rpm, the time being 30 s, and the thickness of the barrier layer being 10 nm.

[0179] After the barrier layer is deposited, a second separation groove is made by laser with a width of 50 μm, and the hole transport layer, light absorption layer, electron transport layer and barrier layer are etched away to expose the first electrode layer;

[0180] The above film was placed in the evaporation apparatus and the vacuum degree of evaporation was 5×10 -4Pa, evaporating 80nm of metal electrode Cu at a rate of 0.1A / s as the second electrode layer, and the metal copper simultaneously fills the second separation groove and is connected with the first electrode layer exposed at the bottom of the second separation groove;

[0181] A third separation groove is manufactured on the second electrode layer by using laser, and all functional layer films on the first electrode layer are etched away to obtain a solar cell module.

[0182] Embodiment 21

[0183] The manufacturing method of solar cell monomer is as follows:

[0184] The specification is 2.0×2.0cm 2 The FTO conductive glass was cut by laser etching to remove 0.35 cm of FTO at both ends, exposing the glass substrate.

[0185] The etched FTO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropanol in sequence;

[0186] The FTO conductive glass was blown dry of solvent under a nitrogen gun and placed in a UV ozone machine for further cleaning;

[0187] After spin coating a hole transport layer of 10 mg / mL nickel oxide nanoparticles (aqueous solution as solvent) on the FTO substrate treated with UV-ozone at a rate of 4000 rpm, the hole transport layer was annealed on a hot plate at 100°C for 30 minutes.

[0188] The perovskite precursor solution was spin-coated on the hole transport layer at 1000-5000 rpm / s, annealed at 100°C for 30 min, and cooled to room temperature. The absorption layer was 1.4 MCs 0.05 (FA 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 Perovskite system;

[0189] The electron transport layer PCBM was spin-coated on the perovskite layer at 1500 rpm and annealed at 100 °C for 10 min;

[0190] A 25 nm thick tin dioxide layer was prepared on the electron transport layer using an atomic layer deposition device as a barrier layer. During the atomic layer deposition process, the tin dioxide layer was simultaneously deposited on the upper surface of the electron transport layer and the exposed side surface of the device. The barrier layers deposited on the side surface and the upper surface were both approximately 25 nm thick.

[0191] The above product is placed in a vapor deposition machine to vapor deposit metal electrode Cu to obtain a battery device.

[0192] The preparation methods of Examples 22-23 are basically the same as those of Example 21, except that the components of the deposition are changed; in the atomic layer deposition process of Example 22, Ti(NMe 2 ) 4 is a titanium source, water is an oxygen source, the barrier layer includes titanium dioxide, and ZnMe 2 is the zinc source, water is the oxygen source, and the barrier layer comprises zinc oxide.

[0193] Example 24 Fluorine-doped tin dioxide (FTO) was deposited by magnetron sputtering.

[0194] Examples 25-28 are basically the same as Example 21, except that the thickness of the barrier layer is changed by adjusting the deposition time.

[0195] The preparation methods of Example 29 and Example 21 are basically the same, except that the side of the active layer is shielded during the deposition process so that only an atomic layer of the barrier layer is deposited on the surface of the active layer.

[0196] The preparation method of Example 30 is basically the same as that of Example 21, except that tin dioxide is used as the target material and tin dioxide is deposited by magnetron sputtering.

[0197] The preparation methods of Comparative Example 2 and Example 13 are basically the same, except that the component of the barrier layer in Comparative Example 2 is bathocuproine (BCP), and the deposition method is:

[0198] The BCP barrier layer was prepared by spin coating with a concentration of 5 mg / mL, isopropanol as solvent, a spin coating speed of 4000 rpm, and a time of 30 s;

[0199] The barrier layer is only deposited on the upper surface of the layer and cannot be deposited on the side of the active layer at the same time.

[0200] Test Method

[0201] 1. Photoelectric conversion efficiency test

[0202] The battery performance was tested using Keithley 2400 SMU, AM 1.5G solar radiation test system under a light source of 100 mW / cm2. The photoelectric conversion efficiency was calculated as follows:

[0203] PCE=Pout / Popt

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

[0205] =Voc×Jsc×FF / Popt

[0206] Where Pout(mW / cm 2)、Popt(mW / cm 2 )、Vmpp(V)、Jmpp(mA / cm 2 ), Voc(V) and Jsc(mA / cm 2 ) are the battery operating output power, incident light power, battery maximum power point voltage, battery maximum power point current, open circuit voltage and short circuit current density respectively.

[0207] For a solar cell module, its Jsc is calculated by dividing the short-circuit current by the area of ​​the solar cell module;

[0208] For a solar cell, its Jsc is calculated by dividing the short-circuit current by the solar cell area.

[0209] 2. Stability test

[0210] The solar cell or battery module is placed on a hot stage at 65°C and heated continuously. The change of its photoelectric conversion efficiency with aging time is tracked, and the time required for its photoelectric conversion efficiency to decay to 80% of the initial efficiency is recorded as T80. The size of this parameter indicates the thermal stability of the perovskite solar cell or battery module.

[0211] 3. Hole mobility test

[0212] The principle of hole mobility test is to use the Hall effect to measure the mobility of holes in semiconductor materials. The Hall effect refers to the transverse electric field generated when current passes through semiconductor materials under the action of a magnetic field. This electric field is called the Hall field. The size of the Hall field is related to the current, magnetic field and the properties of the semiconductor material. The Ecopia HMS-3000 Hall effect tester is used to measure the size and direction of the Hall field and calculate the mobility of holes in semiconductor materials.

[0213] 4. Energy level test

[0214] Energy level testing is performed by ultraviolet photoelectron spectroscopy (UPS), which uses ultraviolet light to excite the sample surface, causing photoelectrons to be emitted from the sample surface.

[0215] Sample size: less than 1x1cm 2 , thickness less than 2mm;

[0216] Sample preservation: Ensure that the sample surface is free of contamination before testing;

[0217] Sample preparation: The film sample to be measured needs to be made on a conductive glass substrate and then fixed on the sample stage with conductive tape to ensure good conductivity.

[0218] In the UPS spectrum, the secondary electron cutoff edge E cutoffThe position corresponding to the highest binding energy of the detected electron, that is, the position corresponding to the lowest kinetic energy, is usually combined with the position of the Fermi edge to determine the work function. The HOMO energy level of the film is calculated using UPS, and then the LUMO energy level of the film can be calculated using the band gap.

[0219] 5. XPS test

[0220] After the device was aged for 96 hours, the components on the second electrode side were tested by XPS using an X-ray photoelectron spectroscopy instrument.

[0221] XPS analysis software can compare the peaks of the same element under different test conditions. By comparing the peak position and peak intensity, information such as the content and chemical potential of the relevant elements can be obtained.

[0222] Test Results

[0223] Table 1

[0224]

[0225] Table 2

[0226]

[0227] Table 3

[0228]

[0229] Table 4

[0230]

[0231] As can be seen from Table 1, in Examples 1-11, the barrier layer of the solar cell assembly includes an n-type semiconductor oxide. Compared with the solar cell assembly using bathocuproin as the barrier layer in Comparative Example 1, the thermal stability of the solar cell assembly in the examples is significantly improved.

[0232] As can be seen from Table 2, in Examples 21-30, the barrier layer of the solar cell monomers includes n-type semiconductor oxides. Compared with the solar cell monomers in Comparative Example 2 using bathocuproin as the barrier layer, the thermal stability of the solar cell monomers in the examples is significantly improved.

[0233] Depend on Figure 8 It can be seen that after the solar cell assembly in Example 1 has been aged for 96 hours, the detectable iodine content in the second electrode layer is significantly lower than the iodine content in the second electrode layer of the solar cell assembly in Comparative Example 1. This indicates that the tin oxide in the barrier layer in Example 1 effectively inhibits the diffusion of halogen in the perovskite into the second electrode layer.

[0234] In Example 1, the highest occupied molecular orbital (HOMO) energy level of tin dioxide is -7.8eV, which is lower than the highest occupied molecular orbital energy level of perovskite -5.4eV and the highest occupied molecular orbital energy level of PCBM -6eV, and plays the role of a barrier layer; and the lowest unoccupied molecular orbital (LUMO) energy level of tin dioxide is -4.4eV, which is lower than the lowest unoccupied molecular orbital energy level of perovskite -4eV and the lowest unoccupied molecular orbital energy level of PCBM -4.3eV. Compared with titanium dioxide (LUMO energy level of -4.5eV) and zinc oxide (LUMO energy level of -4.6V) as a barrier layer, the energy level of tin dioxide is more matched with the electron transport layer, and the photoelectric conversion efficiency is further improved.

[0235] The hole mobility of tin dioxide in Example 1 is 21 cm 2 / (Vs), the hole mobility of fluorine-doped tin dioxide in Example 4 is 10 5 cm 2 / (Vs), compared with the fluorine-doped tin dioxide in Example 4, the tin dioxide in Example 1 plays a role in blocking holes, so the photoelectric conversion efficiency of the solar cell module is further improved.

[0236] From the comparison between Example 1 and Example 9, it can be seen that the solar cell assembly including the first extension portion disposed on the side surface of the active layer adjacent to the second separation groove can further improve the thermal stability of the solar cell assembly.

[0237] From the comparison between Example 21 and Example 29, it can be seen that the extension portion disposed on the side of the active layer in the solar cell monomer can play a semi-encapsulation role, further improving the thermal stability of the solar cell monomer.

[0238] From the comparison between Example 1 and Example 10, it can be seen that the solar cell assembly includes a fourth separation groove, so that the end of the longitudinal portion of the second electrode layer can be connected to the first electrode layer on the bottom surface of the second separation groove, which can reduce the series resistance and further improve the photoelectric conversion efficiency of the solar cell assembly.

[0239] From the comparison between Example 1 and Example 11, and between Example 21 and Example 30, it can be seen that the atomic layer deposition method will not cause excessive energy damage to the perovskite layer, which is beneficial to the improvement of the photoelectric conversion efficiency of the solar cell module / monomer. In addition, the barrier layer deposited by the atomic layer deposition method is more dense, which can better inhibit the diffusion of halogen ions in the perovskite layer to the metal electrode, and further improve the thermal stability of the solar cell module / monomer.

[0240] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A solar cell, characterized in that: include: A first electrode layer, an active layer, and a second electrode layer are sequentially stacked, and A barrier layer is located between the active layer and the second electrode layer or between the active layer and the first electrode layer, and the barrier layer comprises an n-type semiconductor oxide.

2. The solar cell according to claim 1, characterized in that The hole mobility of the n-type semiconductor oxide is no more than 1000 cm 2 V -1 s -1 , optional 0.1cm 2 V -1 s -1 -1000cm 2 V -1 s -1 .

3. The solar cell according to claim 1 or 2, characterized in that: The n-type semiconductor oxide includes at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

4. The solar cell according to any one of claims 1 to 3, characterized in that The thickness of the barrier layer is 5nm-35nm, and can be optionally 10nm-30nm.

5. The solar cell according to any one of claims 1 to 4, characterized in that The barrier layer is disposed between the second electrode layer and the active layer.

6. The solar cell according to any one of claims 1 to 5, characterized in that The barrier layer further includes an extension portion disposed on at least one side surface of the active layer.

7. The solar cell according to any one of claims 1 to 6, characterized in that The barrier layer is prepared by atomic layer deposition.

8. The solar cell according to any one of claims 1 to 7, characterized in that The active layer includes a light absorbing layer. Optionally, the light absorbing layer includes a perovskite compound.

9. The solar cell according to any one of claims 1 to 8, characterized in that The active layer further includes an electron transport layer, and the electron transport layer is arranged between the light absorbing layer and the blocking layer.

10. The solar cell according to any one of claims 1 to 9, characterized in that: The active layer further comprises a hole transport layer, and the hole transport layer is arranged on a side of the light absorbing layer away from the blocking layer.

11. The solar cell according to any one of claims 1 to 10, characterized in that The highest occupied molecular orbital (HOMO) energy level of the n-type semiconductor oxide is lower than the highest occupied molecular orbital (HOMO) energy level of the light absorbing layer.

12. A method for preparing a solar cell, characterized in that: The preparation method comprises: providing a first electrode layer; forming an active layer on at least one side of the first electrode layer; forming a barrier layer on a side of the active layer away from the first electrode layer; forming a second electrode layer on a side of the barrier layer away from the first electrode layer; The barrier layer includes an n-type semiconductor oxide, and optionally includes at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

13. The preparation method according to claim 12, characterized in that: The barrier layer further includes an extension portion disposed on at least one side surface of the active layer.

14. The preparation method according to claim 12 or 13, characterized in that: The barrier layer is formed by atomic layer deposition.

15. A solar cell module, characterized in that: It comprises a first electrode layer, an active layer, a barrier layer, and a second electrode layer stacked in sequence, Wherein, the barrier layer comprises an n-type semiconductor oxide, and optionally comprises at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

16. The solar cell assembly according to claim 15, characterized in that: The first electrode layer includes a plurality of conductive blocks that are not interconnected, and a first separation groove is provided between adjacent conductive blocks; The active layer includes a plurality of active blocks, a second separation groove is provided between adjacent active blocks, the bottom surface of the second separation groove is provided on the first electrode layer, and the opening of the second separation groove is provided on the upper surface of the active layer; The second electrode layer is disposed on the barrier layer, the second electrode layer further having a longitudinal portion extending toward the first electrode layer, the longitudinal portion passing through the second separation groove, and a terminal end of the longitudinal portion connected to the bottom surface of the second separation groove; The solar cell assembly further includes a third separation groove, wherein an opening of the third separation groove is disposed on the upper surface of the second electrode layer, and a bottom surface of the third separation groove is disposed on the first electrode layer.

17. The solar cell assembly according to claim 15 or 16, characterized in that: The barrier layer at least includes a first horizontal portion located on the upper surface of the active block and a first extending portion extending toward the first electrode, and the first extending portion is disposed on at least one side surface of the active layer adjacent to the second separation groove.

18. The solar cell assembly according to any one of claims 15 to 17, characterized in that: The barrier layer further includes a second horizontal portion located at the bottom surface of the second separation groove; A fourth separation groove is provided on the second horizontal portion, and a longitudinal portion of the second electrode layer passes through the fourth separation groove so that an end thereof is connected to the first electrode layer on the bottom surface of the second separation groove.

19. The solar cell assembly according to claim 18, characterized in that: The width of the fourth separation groove is smaller than the width of the second separation groove.

20. The solar cell assembly according to any one of claims 15 to 19, characterized in that: The barrier layer is prepared by atomic layer deposition; optionally, the thickness of the barrier layer is 5nm-35nm, optionally 10nm-30nm.

21. The solar cell assembly according to any one of claims 15 to 20, characterized in that: The active layer includes a light absorbing layer, Optionally, the light absorbing layer comprises a perovskite compound; Optionally, the active layer further comprises an electron transport layer, and the electron transport layer is arranged between the light absorbing layer and the blocking layer; Optionally, the active layer further includes a hole transport layer, and the hole transport layer is arranged between the battery light absorption layer and the first electrode layer.

22. A method for preparing a solar cell module, characterized in that: The preparation method comprises: providing a first electrode layer; forming at least one first separation groove on the first electrode layer, wherein the first separation groove divides the first electrode layer into a plurality of conductive blocks that are not connected to each other; forming an active layer on at least one side of the first electrode layer; forming at least one second separation groove on the active layer, wherein the bottom surface of the second separation groove is disposed on the first electrode layer, and the opening of the second separation groove is disposed on the upper surface of the active layer; forming a barrier layer on a side of the active layer away from the first electrode layer; forming a second electrode layer on a side of the barrier layer away from the first electrode layer; The second electrode layer has a longitudinal portion extending toward the first electrode layer, the longitudinal portion fills the second separation groove, and a terminal end of the longitudinal portion is connected to the first electrode layer at the bottom of the second separation groove; forming a third separation groove, wherein an opening of the third separation groove is disposed on the upper surface of the second electrode layer, and a bottom surface of the third separation groove is disposed on the first electrode layer; The barrier layer includes an n-type semiconductor oxide, and optionally includes at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

23. The preparation method according to claim 22, characterized in that: The barrier layer is formed at least on an upper surface of the active block and at least one side surface of the active block adjacent to the second separation groove.

24. The preparation method according to claim 22 or 23, characterized in that: The barrier layer is prepared by atomic layer deposition.

25. The preparation method according to any one of claims 22 to 24, characterized in that: The barrier layer is also formed on the bottom surface of the second separation groove; forming a fourth separation groove on the barrier layer located at the bottom surface of the second separation groove, The longitudinal portion of the second electrode layer passes through the fourth separation groove, and the end of the longitudinal portion is connected to the first electrode layer at the bottom surface of the second separation groove.

26. An electrical equipment, characterized in that: A solar cell comprising the solar cell described in any one of claims 1 to 11, or a solar cell prepared by the preparation method described in any one of claims 12 to 14, or a solar cell module described in any one of claims 15 to 21, or a solar cell module prepared by the preparation method described in any one of claims 22 to 25.

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