Solar cell and manufacturing method therefor, solar cell assembly and manufacturing method therefor, and electric device

Abstract

The present application provides a solar cell and a manufacturing method therefor, a solar cell assembly and a manufacturing method therefor, and an electric device. The solar cell comprises: a first electrode layer, an active layer, a second electrode layer, and a barrier layer which are stacked in sequence; 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 compared with a conventional material of the barrier layer such as bathocuproine, the n-type semiconductor oxide has higher heat resistance, so that the solar cell has higher heat stability by using the n-type semiconductor oxide as the barrier layer.

Description

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

[0001] Cross-references

[0002] This application claims priority to Chinese Patent Application No. 202310967471.9, filed on August 2, 2023, entitled “Solar Cells and Methods for Manufacturing Them, Solar Cell Modules and Methods for Manufacturing Them, and Electrical Equipment,” which is incorporated herein by reference in its entirety. Technical Field

[0003] 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

[0004] 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 and renewable energy has gradually become an alternative to non-renewable energy sources to promote social and industrial development. Among them, solar cell devices are widely used due to their environmental friendliness and ability to output electricity when exposed to sunlight.

[0005] However, in the related art, solar cell devices have poor heat resistance, resulting in a short service life, which limits their further promotion and application.

[0006] Summary of the Invention

[0007] 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.

[0008] 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 blocking layer stacked in sequence, wherein the blocking layer is located between the active layer and the second electrode layer or between the active layer and the first electrode layer, and the blocking layer comprises an n-type semiconductor oxide.

[0009] 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 can make the solar cell have higher thermal stability.

[0010] 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 .

[0011] 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.

[0012] In any embodiment, the n-type semiconductor oxide includes at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0013] In any embodiment, the n-type semiconductor oxide comprises tin oxide.

[0014] Tin oxide also has 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.

[0015] In any embodiment, the thickness of the barrier layer is 5 nm to 35 nm, and optionally 10 nm to 30 nm.

[0016] When the thickness of the barrier layer is within an appropriate range, the thermal stability and photoelectric conversion efficiency of the solar cell can be improved simultaneously.

[0017] In any embodiment, the barrier layer is disposed between the second electrode layer and the active layer.

[0018] There is an electric field in the active layer (such as perovskite compound), and halogen anions are prone to diffusion under the action of the electric field. Halogen anions have a low diffusion rate in n-type semiconductors. Using n-type semiconductor oxide 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.

[0019] In any embodiment, the barrier layer further includes an extension portion disposed on at least one side surface of the active layer.

[0020] The extension portion arranged on at least one side of the active layer can form a semi-encapsulated structure for the solar cell, effectively blocking water and oxygen in the air from entering the active layer, especially preventing water and oxygen from aging the light-absorbing layer in the active layer, slowing down the degradation of the perovskite material in the external environment, and improving the photoelectric conversion efficiency and stability of the device.

[0021] In any embodiment, the portions of the barrier layer are formed simultaneously.

[0022] 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 damage to the active layer caused by multiple successive depositions.

[0023] In any embodiment, the barrier layer is prepared by atomic layer deposition.

[0024] The thin film prepared by the atomic layer deposition method 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 the metal in the electrode layer by halogen anions, 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 or angle. The reaction precursor can be freely adsorbed on any exposed surface of the active layer, realizing the simultaneous formation of the barrier layer in all directions, which has the characteristics of high production efficiency and low cost.

[0025] 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, thereby improving the photoelectric conversion efficiency and device stability of solar cells.

[0026] In any embodiment, the active layer comprises a light absorbing layer, and optionally, the light absorbing layer comprises a perovskite compound.

[0027] 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.

[0028] The blocking layer is arranged on the surface of the electron transport layer. Compared with the blocking layer being directly arranged on the surface of the light absorbing layer, it can effectively reduce the damage to the light absorbing layer caused by the deposition of the blocking layer and reduce the negative impact on the photoelectric conversion efficiency.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] The second aspect of the present application provides a method for preparing a solar cell, the 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 facing away from the first electrode layer; forming a second electrode layer on a side of the barrier layer facing away from the first electrode layer; the barrier layer comprising an n-type semiconductor oxide, optionally comprising at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0033] In any embodiment, the barrier layer further includes an extension portion disposed on at least one side surface of the active layer.

[0034] In any embodiment, the barrier layer is formed by atomic layer deposition.

[0035] A third aspect of the present application provides a solar cell assembly, 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.

[0036] Using an n-type semiconductor oxide as a barrier layer can prevent holes from migrating toward the cathode. As an inorganic material, n-type semiconductor oxide has higher heat resistance than traditional barrier layer materials such as bathocuprol, resulting in higher thermal stability for solar cell modules.

[0037] In any embodiment, 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, and 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 provided on the blocking 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 provided on the upper surface of the second electrode layer, and the bottom surface of the third separation groove is provided on the first electrode layer.

[0038] 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.

[0039] In any embodiment, the barrier layer includes at least 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 provided on at least one side surface of the active layer adjacent to the second separation trench.

[0040] 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, slowing down the corrosion of the second electrode layer and improving the stability and photoelectric conversion efficiency of the solar cell module.

[0041] 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.

[0042] 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, which can reduce the series resistance between solar cell monomers and improve the photoelectric conversion efficiency of the solar cell module.

[0043] In any embodiment, the width of the fourth separation groove is smaller than the width of the second separation groove.

[0044] The above-mentioned arrangement enables the end of the longitudinal portion of the second electrode layer to be connected to the first electrode layer on the bottom surface 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.

[0045] In any embodiment, the barrier layer is prepared by atomic layer deposition. Optionally, the barrier layer has a thickness of 5 nm to 35 nm, and optionally 10 nm to 30 nm.

[0046] In any embodiment, the active layer includes a light-absorbing layer. Optionally, the light-absorbing layer includes a perovskite compound. Optionally, 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; optionally, the active layer further includes a hole transport layer, and the hole transport layer is arranged between the battery light-absorbing layer and the first electrode layer.

[0047] 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 a side of the active layer facing away from the first electrode layer; forming a second electrode layer on a side of the barrier layer facing 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 comprising an n-type semiconductor oxide, optionally comprising at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide.

[0048] In any embodiment, the barrier layer is formed on at least the upper surface of the active block and at least one side surface of the active block adjacent to the second separation groove.

[0049] In any embodiment, the barrier layer is prepared by atomic layer deposition.

[0050] 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.

[0051] 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.

[0052] 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

[0053] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiment below. The accompanying drawings are for illustration purposes only and are not to be considered as limiting the present application. The same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0054] FIG1 shows a schematic cross-sectional structure diagram of a solar cell provided in some embodiments of the present application;

[0055] FIG2 shows a schematic cross-sectional structure diagram of a solar cell provided in some embodiments of the present application;

[0056] FIG3 shows a schematic cross-sectional structure diagram of a solar cell provided in some embodiments of the present application;

[0057] FIG4 shows a schematic cross-sectional structure diagram of a solar cell provided in some embodiments of the present application;

[0058] FIG5 shows a schematic cross-sectional structure diagram of a solar cell provided in some embodiments of the present application;

[0059] FIG6 shows an energy level diagram of a solar cell provided by some embodiments of the present application;

[0060] FIG7 shows a schematic cross-sectional structure diagram of a solar cell assembly provided in some embodiments of the present application;

[0061] FIG8 shows the I in the second electrode layer of the solar cell assembly after aging in Example 1 and Comparative Example 1 of the present application. 3d X-ray photoelectron spectroscopy (XPS) spectrum.

[0062] The accompanying drawings in the specific implementation manner are as follows:

[0063] Solar cells 1-1, 1-2, 1-3, 1-4, 1-5;

[0064] Solar cell module 2;

[0065] first electrode layers 10, 20;

[0066] Active layers 11 and 21, light absorbing layer 111, electron transport layer 112, hole transport layer 113

[0067] Second electrode layers 12, 22; longitudinal portion 221;

[0068] Barrier layers 13, 23; extension portion 131; first horizontal portion 232; first extension portion 231; second horizontal portion 233

[0069] 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

[0070] The following embodiments of the technical solution of the present application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application and are therefore only examples and are not intended to limit the scope of protection of the present application.

[0071] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art 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" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0072] In the description of the embodiments of this application, the technical terms "first," "second," etc. are used only to distinguish different objects and should not be understood to indicate or imply relative importance or to implicitly indicate the quantity, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, the meaning of "plurality" is more than two, unless otherwise specifically defined.

[0073] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0074] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0075] 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).

[0076] In the description of the embodiments of the present application, the technical terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings. They 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 device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, they should not be understood as limiting the embodiments of the present application.

[0077] In the description of the embodiments of the present application, unless otherwise expressly specified or limited, technical terms such as "installed," "connected," "connected," and "fixed" should be understood in a broad sense. For example, they can refer to fixed connections, detachable connections, or integration; mechanical connections or electrical connections; direct connections or indirect connections through an intermediate medium; and internal connections between two components or interactions between two components. Those skilled in the art can understand the specific meanings of the above terms in the embodiments of the present application based on specific circumstances.

[0078] 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, 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, bathocuproine is an organic substance that easily agglomerates under heat, resulting in poor thermal stability of solar cells.

[0079] Based on this, as shown in Figures 1 and 2, 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 being 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.

[0080] 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.

[0081] In some embodiments, the blocking layer is a hole blocking layer.

[0082] 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.

[0083] In some embodiments, the hole mobility of the n-type semiconductor oxide is no more than 1000 cm2V-1s-1. In some embodiments, the hole mobility of the n-type semiconductor oxide is 0.1 cm2V-1s-1 to 1000 cm2V-1s-1.

[0084] Hole mobility refers to the rate at which holes move under the action of an electric field.

[0085] In some embodiments, the hole mobility of the n-type semiconductor oxide may be selected to be 0.1 cm2V-1s-1, 1 cm2V-1s-1, 10 cm2V-1s-1, 100 cm2V-1s-1, 500 cm2V-1s-1, 1000 cm2V-1s-1, or any value therebetween.

[0086] 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.

[0087] In some embodiments, the n-type semiconductor oxide comprises at least one of tin oxide, titanium oxide, zinc oxide, indium oxide, and gallium oxide. In some embodiments, the n-type semiconductor oxide comprises tin oxide.

[0088] Tin oxide also has 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.

[0089] In some embodiments, the barrier layer 13 has a thickness of 5 nm to 35 nm. In some embodiments, the barrier layer 13 has a thickness of 10 nm to 30 nm.

[0090] When the thickness of the barrier layer is within an appropriate range, the thermal stability and photoelectric conversion efficiency of the solar cell can be improved simultaneously.

[0091] In some embodiments, the solar cells 1-1 and 1-2 may include perovskite cells, fuel cell-sensitized solar cells, etc. In some embodiments, the solar cells 1-1 and 1-2 may include perovskite cells.

[0092] In some embodiments, as shown in FIG. 3 and FIG. 4 , the active layer 11 includes a light absorbing layer 111 . In some embodiments, the light absorbing layer 111 includes a perovskite compound.

[0093] In some embodiments, the thickness of the light absorbing layer 111 is 400 nm to 1000 nm. In some embodiments, the thickness of the light absorbing layer 111 can be 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range thereof. In some embodiments, the thickness of the light absorbing layer 111 is 500 nm to 900 nm.

[0094] In some embodiments, the band gap of the perovskite compound is 1.20 eV to 2.30 eV. In some embodiments, 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.

[0095] In some embodiments, the perovskite compound comprises a perovskite metal halide; the chemical formula of the perovskite metal halide is ABX3; wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion. In some embodiments, A comprises Cs + , K + , Rb + , one or more of monovalent amine cations and monovalent amidino cations. Non-limiting examples of monovalent amine cations include CH3NH3 + (Methylamine, MA + ), ammonium (NH4 + ). Non-limiting examples of monovalent amidinium cations include NH2CH=NH2 + (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 .

[0096] In some embodiments, as shown in FIG. 3 and FIG. 4 , 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 .

[0097] 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 61BM), [6,6]-phenyl C71 butyric acid methyl ester (PC 71 BM), fullerene.

[0098] The blocking layer 13 is arranged on the surface of the electron transport layer 112. Compared with the blocking layer 13 being directly arranged on the surface of the light absorbing layer 111, it can effectively reduce the damage to the light absorbing layer 111 caused by the deposition of the blocking layer 13 and reduce the negative impact on the photoelectric conversion efficiency.

[0099] In some embodiments, as shown in FIG. 3 and FIG. 4 , the active layer 11 further includes a hole transport layer 113 . The hole transport layer 113 is disposed on a side of the light absorbing layer 111 facing away from the blocking layer 13 .

[0100] 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 (P3HT), 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(styrenesulfonate) (PEDOT:PSS), polythiophene, nickel oxide (NiOx), molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (Cu2O).

[0101] In some embodiments, the first electrode layer 10 is a transparent electrode layer, and the second electrode layer 12 is a back electrode layer.

[0102] 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).

[0103] In some embodiments, the thickness of the first electrode layer 10 is 200 nm to 1000 nm. In some embodiments, the thickness of the first electrode layer 10 can be 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range thereof.

[0104] In some embodiments, the second electrode layer 12 is typically 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.

[0105] In some embodiments, the thickness of the second electrode layer 12 is 20 nm to 200 nm. In some embodiments, the thickness of the second electrode layer 12 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.

[0106] In some embodiments, as shown in FIG3 , the solar cell 1 - 3 is an inverted pin perovskite cell, comprising a first electrode layer 10 , a hole transport layer 113 , a light absorbing layer 111 , an electron transport layer 112 , a blocking layer 13 , and a second electrode layer 12 stacked in sequence.

[0107] In some embodiments, as shown in FIG4 , the solar cell 1-4 is a formal nip perovskite cell, comprising a first electrode layer 10 , a blocking layer 13 , an electron transport layer 112 , a light absorbing layer 111 , a hole transport layer 113 , and a second electrode layer 12 stacked in sequence.

[0108] In some embodiments, as shown in FIG. 3 , the barrier layer 13 is disposed between the second electrode layer 12 and the active layer 11 .

[0109] 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 the solar cell.

[0110] In some embodiments, as shown in FIG. 5 , the barrier layer 13 further includes an extension portion 131 disposed on at least one side surface of the active layer 11 .

[0111] In some embodiments, the thickness of the extension portion 131 of the barrier layer 13 is 5 nm to 35 nm. In some embodiments, the thickness is 10 nm to 30 nm. In some embodiments, the thickness of the extension portion 131 of the barrier layer 13 is 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, or any range thereof.

[0112] The extension portion 131 arranged on at least one side of the active layer 11 can form a semi-encapsulated structure for the solar cells 1-5, effectively blocking water and oxygen in the air from entering the active layer 11, especially preventing water and oxygen from aging the light-absorbing layer 111, slowing down the degradation of the perovskite material in the external environment, and improving the photoelectric conversion efficiency and stability of the device.

[0113] In some embodiments, portions of barrier layer 13 are formed simultaneously.

[0114] The various parts of the barrier layer 13 are formed simultaneously during 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 damage to the active layer 11 due to multiple depositions.

[0115] In some embodiments, the barrier layer 13 is prepared by atomic layer deposition.

[0116] 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.

[0117] The thin film prepared by the atomic layer deposition method has high density and can effectively block the diffusion of halogen anions in the light-absorbing layer 111 to the second electrode layer 12. In particular, it can alleviate the corrosion of the metal in the electrode layer by halogen anions, effectively improving the stability and photoelectric conversion efficiency of the solar cell. 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 by the atomic layer deposition method is not restricted by direction or angle. The reaction precursor can be freely adsorbed on any surface exposed by 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.

[0118] 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.

[0119] As shown in FIG6 , 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 , and can block holes from diffusing from the highest occupied molecular orbital of the light absorbing layer 111 to the highest occupied molecular orbital of the n-type semiconductor oxide, thereby acting as a blocking layer.

[0120] 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.

[0121] As shown in Figure 6, 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 holes from diffusing 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 acts as 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 transport efficiency, and facilitating the improvement of the photoelectric conversion efficiency of the solar cell.

[0122] The second aspect of the present application provides a method for preparing a solar cell. Please continue to refer to Figure 3. The 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 facing away from the first electrode layer 10; forming a second electrode layer 12 on the side of the barrier layer 13 facing 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.

[0123] In some embodiments, the barrier layer 13 further includes an extension portion 131 disposed on at least one side surface of the active layer 11 .

[0124] In some embodiments, the barrier layer 13 is formed by atomic layer deposition.

[0125] In some embodiments, the barrier layer 13 is formed by atomic layer deposition using a metal source and an oxygen source.

[0126] In some embodiments, the metal source includes at least one of an organotin source, an organotitanium source, and an organozinc source.

[0127] In some embodiments, the tin source comprises an organotin source, optionally tetrakis(dimethylamino)tin.

[0128] In some embodiments, the oxygen source includes at least one of water and ozone.

[0129] In a third aspect of the present application, as shown in FIG6 , 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.

[0130] Solar cell modules are composed of several solar cell modules connected in series or parallel. Using an n-type semiconductor oxide as a barrier layer prevents holes from migrating toward the cathode. As an inorganic material, n-type semiconductor oxides offer higher heat resistance than traditional barrier materials such as bathocuprol, resulting in higher thermal stability for solar cell modules.

[0131] In some embodiments, with continued reference to FIG6 , the first electrode layer 20 includes a plurality of conductive blocks that are not interconnected, and a first separation groove P-1 is provided between adjacent conductive blocks; the active layer 21 includes a plurality of active blocks, and a second separation groove P-2 is provided between adjacent active blocks, the bottom surface of the second separation groove P-2 is provided on the first electrode layer 20, and the opening of the second separation groove P-2 is provided on the upper surface of the active layer 21; the second electrode layer 22 is provided 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 provided on the upper surface of the second electrode layer 22, and the bottom surface of the third separation groove P-3 is provided on the first electrode layer 20.

[0132] 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.

[0133] 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 . The first extension portion 231 is disposed on at least one side of the active layer 21 adjacent to the second separation trench P- 2 .

[0134] 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 toward the second electrode layer 22 , thereby slowing down the corrosion of the second electrode layer 22 and improving the stability and photoelectric conversion efficiency of the solar cell module.

[0135] 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.

[0136] 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 on the bottom surface of the second separation groove P-2, which can reduce the series resistance between solar cell units and improve the photoelectric conversion efficiency of the solar cell module.

[0137] In some embodiments, the width of the fourth separation groove P-4 is smaller than the width of the second separation groove P-2.

[0138] The above-mentioned setting 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 setting 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 blocking role and will not have other negative effects on the photoelectric conversion efficiency and stability of the solar cell module.

[0139] In some embodiments, the barrier layer 23 is prepared by atomic layer deposition.

[0140] 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 thin 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 the metal in the electrode layer by halogen anions, effectively improving the stability and photoelectric conversion efficiency of the solar cell. 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 by the atomic layer deposition method is not restricted by direction or angle. The reaction precursor can be freely adsorbed on any exposed side of the active layer, realizing the simultaneous formation of the first extension portion 231, the first horizontal portion 232 and the second horizontal portion 233 of the barrier layer, with the characteristics of high production efficiency and low cost.

[0141] In some embodiments, the barrier layer 23 has a thickness of 5 nm to 35 nm. In some embodiments, the barrier layer 23 has a thickness of 10 nm to 30 nm.

[0142] 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.

[0143] In some embodiments, the active layer 21 includes a light absorbing layer.

[0144] In some embodiments, the light absorbing layer 211 includes a perovskite compound;

[0145] In some embodiments, the active layer 21 further includes an electron transport layer 212 , which is disposed between the light absorbing layer 211 and the blocking layer 23 .

[0146] In some embodiments, the active layer 21 further includes a hole transport layer 213 , which is disposed between the light absorbing layer 211 and the first electrode layer 20 .

[0147] The 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; forming a barrier layer 23 on the barrier ... barrier layer 21; forming a barrier layer 23 on the side of the active layer 21 away from the first electrode layer 20; forming a barrier layer 23 on the barrier layer 21; forming 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.

[0148] Unlike the existing technology, 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.

[0149] In some embodiments, the barrier layer 23 is formed on at least 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 .

[0150] In some embodiments, the barrier layer 23 is prepared by atomic layer deposition.

[0151] 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.

[0152] In some embodiments, at least one of the first separation trench P-1, the second separation trench P-2, the third separation trench P-3, and the fourth separation trench P-4 is formed by laser cutting.

[0153] Laser cutting is precise and efficient, and can effectively improve the processing accuracy of solar cell modules and reduce manufacturing costs.

[0154] The fifth aspect of the present application provides an electrical device, including a solar cell in any embodiment or a solar cell prepared by the preparation method in any embodiment or a solar cell component in any embodiment or a solar cell component prepared by the preparation method in any embodiment.

[0155] In some embodiments, a solar cell or solar cell module can be used as a power generation device for an electrical device. The types of power generation devices may include, but are not limited to, integrated power generation.

[0156] The electrical devices may include, but are not limited to, mobile devices such as mobile phones, tablet computers, laptop computers, calculators, watches, cars, electric trains, ships, satellites, power generation systems, etc.

[0157] The location of the power generation device may include but is not limited to the roof, back panel, etc. of the car.

[0158] The following examples describe the present disclosure in more detail and are intended to be illustrative only, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, 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 used directly without further processing, and all instruments used in the examples are commercially available.

[0159] Example

[0160] Preparation method

[0161] Example 1

[0162] The present invention provides a method for manufacturing a solar cell module, which comprises the following steps:

[0163] Preparation of the first electrode layer: ultrasonically clean the etched FTO conductive glass several times with water, acetone, and isopropyl alcohol, and then blow dry with nitrogen gas for use as the first electrode layer;

[0164] Using a laser to create a first separation groove (P1) on a cleaned FTO substrate, etching away the FTO conductive layer to expose the substrate;

[0165] Preparation of the hole transport layer: A transparent conductive glass substrate was treated with UV ozone, and then a nickel oxide layer with a thickness of approximately 30 nm was magnetron sputtered. The layer was annealed at 300°C for 60 minutes to obtain a hole transport layer.

[0166] Preparation of the perovskite layer: The perovskite light absorption layer was prepared using 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 μL of anti-solvent was added dropwise around the 10th second 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.

[0167] 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 antisolvent was anisole;

[0168] Preparation of electron transport layer: put the film with perovskite layer into the evaporation apparatus 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 ;

[0169] A second separation groove with a width of 50 μm is manufactured on the electron transport layer 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;

[0170] A layer of tin dioxide with a thickness of approximately 25 nm was prepared as a barrier layer on a substrate having a second separation groove using atomic layer deposition technology; the barrier layer was deposited on any exposed surface on the substrate having 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 was as follows: the tin source used was tetrakis(dimethylamino)tin (TDMASn), the oxygen source used was water, the pulse and purge times were TDMASn 0.5 s, nitrogen 3 s, water 0.5 s, nitrogen 5 s, the local pressure was 50 mtorr, the flushing flow rate was 5000 sccm, the reaction temperature was 100°C, and the source temperature was 45°C.

[0171] 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 form 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 of the second separation groove;

[0172] The film with barrier layer was placed into the evaporation apparatus and the vacuum degree of evaporation was set to 5×10 -4 Pa, evaporating 80nm of Cu metal electrode at a rate of 0.1A / s as the second electrode layer. The metal copper also fills the second separation groove and is connected to the first electrode layer exposed at the bottom of the second separation groove.

[0173] 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.

[0174] The preparation method of Example 2-3 is basically the same as that of Example 1, except that the component of the barrier layer is changed; in the atomic layer deposition process of Example 2, Ti(NMe2)4 is used as the titanium source, water is used as the oxygen source, and the barrier layer includes titanium dioxide; in the atomic layer deposition process of Example 3, ZnMe2 is used as the zinc source, water is used as the oxygen source, and the barrier layer includes zinc oxide.

[0175] In Example 4, fluorine-doped tin dioxide was used as the target material, and a 25 nm thick impedance layer was prepared by magnetron sputtering deposition.

[0176] The preparation methods of Examples 5-8 are basically 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;

[0177] The preparation method of Example 9 is basically the same as that of Example 1, except that the side surfaces of the active layer are 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 its side surfaces;

[0178] 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;

[0179] The preparation method of Example 11 is basically the same as that of Example 1, except that the barrier layer tin dioxide is deposited by magnetron sputtering using tin dioxide as a target material.

[0180] 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 bathocuproine (BCP), and the deposition method of the barrier layer is:

[0181] The BCP barrier layer was prepared by spin coating with a concentration of 5 mg / mL, isopropanol as the solvent, a spin coating speed of 4000 rpm, a time of 30 s, and a barrier layer thickness of 10 nm.

[0182] After depositing the barrier layer, a second separation groove with a width of 50 μm was made using laser, and the hole transport layer, light absorption layer, electron transport layer and barrier layer were etched away to expose the first electrode layer.

[0183] The above film was placed in the evaporation apparatus and the vacuum degree of evaporation was set to 5×10 -4 Pa, evaporating 80nm of Cu metal electrode at a rate of 0.1A / s as the second electrode layer. The metal copper also fills the second separation groove and is connected to the first electrode layer exposed at the bottom of the second separation groove.

[0184] 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.

[0185] Example 21

[0186] The manufacturing method of solar cell monomer is as follows:

[0187] Take the size of 2.0×2.0cm 2 The FTO conductive glass was removed by laser etching at both ends to remove 0.35 cm of FTO, exposing the glass substrate;

[0188] The etched FTO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropyl alcohol in sequence;

[0189] The FTO conductive glass was blown dry of solvent under a nitrogen gun and placed in a UV ozone machine for further cleaning;

[0190] A hole transport layer of 10 mg / mL nickel oxide nanoparticles (aqueous solution as solvent) was spin-coated on the UV-ozone treated FTO substrate at a speed of 4000 rpm and then annealed on a hot plate at 100°C for 30 minutes.

[0191] The perovskite precursor solution was spin-coated on the hole transport layer at 1000-5000 rpm / s, annealed at 100 ° C for 30 minutes, 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 )3Perovskite system;

[0192] The electron transport layer PCBM was spin-coated on the perovskite layer at 1500 rpm and annealed at 100 °C for 10 min;

[0193] A 25nm 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 and upper surfaces were both approximately 25nm thick.

[0194] The above product is placed in an evaporation machine, and a metal electrode Cu is evaporated to obtain a battery device.

[0195] The preparation methods of Examples 22-23 are basically the same as those of Example 21, except that the deposited components are changed; in the atomic layer deposition process of Example 22, Ti(NMe2)4 is used as the titanium source, water is used as the oxygen source, and the barrier layer includes titanium dioxide; in the atomic layer deposition process of Example 23, ZnMe2 is used as the zinc source, water is used as the oxygen source, and the barrier layer includes zinc oxide.

[0196] In Example 24, fluorine-doped tin dioxide (FTO) was deposited by magnetron sputtering.

[0197] 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.

[0198] The preparation method of Example 29 is basically the same as that of Example 21, 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.

[0199] 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.

[0200] 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:

[0201] 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.

[0202] 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.

[0203] Test Method

[0204] 1. Photoelectric conversion efficiency test

[0205] The battery performance was tested using a Keithley 2400SMU, AM 1.5G solar radiation test system under a 100mW / cm2 light source. The photoelectric conversion efficiency was calculated as follows: PCE = Pout / Popt = Voc × Jsc × (Vmpp × Jmpp) / (Voc × Jsc × Popt) = 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 solar cell modules, 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 plate at 65°C and continuously heated. The change in 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 hole mobility test utilizes 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 a semiconductor material under the influence of a magnetic field. This field is called the Hall field. The magnitude 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 magnitude and direction of the Hall field and calculate the hole mobility in the semiconductor material.

[0213] 4. Energy level test

[0214] Energy level measurements are performed using 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 cutoff The work function is determined by combining the position of the Fermi edge with the position of the highest binding energy of the detected electron, i.e., the position with the lowest kinetic energy. The HOMO energy level of the film is calculated using UPS, and the LUMO energy level of the film can then 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 relevant element content and chemical potential can be obtained.

[0222] Test results

[0223] Table 1

[0224] Table 2

[0225] Table 3

[0226] Table 4

[0227] As shown in Table 1, in Examples 1-11, the barrier layer of the solar cell modules includes an n-type semiconductor oxide. Compared with the solar cell module in Comparative Example 1 using bathocuproin as the barrier layer, the thermal stability of the solar cell modules in the Examples is significantly improved.

[0228] As shown in Table 2, the barrier layers of the solar cell units in Examples 21-30 include n-type semiconductor oxides. Compared to the solar cell units in Comparative Example 2 using bathocuproin as the barrier layer, the thermal stability of the solar cell units in the Examples is significantly improved.

[0229] As shown in Figure 8 , after aging for 96 hours, the detectable iodine content in the second electrode layer of the solar cell module in Example 1 was significantly lower than that in the second electrode layer of the solar cell module in Comparative Example 1. This indicates that the tin oxide in the barrier layer in Example 1 effectively inhibited the diffusion of halogens from the perovskite into the second electrode layer.

[0230] In Example 1, the highest occupied molecular orbital (HOMO) energy level of tin dioxide is -7.8 eV, which is lower than the highest occupied molecular orbital energy level of perovskite -5.4 eV and the highest occupied molecular orbital energy level of PCBM -6 eV, and acts as a barrier layer; and the lowest unoccupied molecular orbital (LUMO) energy level of tin dioxide is -4.4 eV, which is lower than the lowest unoccupied molecular orbital energy level of perovskite -4 eV and the lowest unoccupied molecular orbital energy level of PCBM -4.3 eV. Compared with titanium dioxide (LUMO energy level of -4.5 eV) and zinc oxide (LUMO energy level of -4.6 V) 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.

[0231] 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.

[0232] 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.

[0233] From the comparison between Example 21 and Example 29, it can be seen that the extension portion provided 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.

[0234] From the comparison between Example 1 and Example 10, it can be seen that the solar cell assembly includes a fourth separation groove, which enables the end of the longitudinal portion of the second electrode layer to be connected to the first electrode layer on the bottom surface of the second separation groove, thereby reducing the series resistance and further improving the photoelectric conversion efficiency of the solar cell assembly.

[0235] Comparisons of Examples 1 and 11, and 21 and 30, show that atomic layer deposition (ALD) does not cause excessive energy damage to the perovskite layer, thus improving the photoelectric conversion efficiency of solar cell modules and cells. Furthermore, the barrier layer deposited by ALD is denser, better inhibiting the diffusion of halide ions from the perovskite layer to the metal electrode, further improving the thermal stability of the solar cell modules and cells.

[0236] 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 make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions 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, wherein: 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, wherein: 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, wherein: 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, wherein: 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, wherein: 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, wherein: 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, wherein: The barrier layer is prepared by atomic layer deposition.

8. The solar cell according to any one of claims 1 to 7, wherein: 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, wherein: 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, wherein: 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, wherein: 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, wherein: 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, wherein: 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, wherein: The barrier layer is formed by atomic layer deposition.

15. A solar cell module, wherein: 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 module according to claim 15, wherein: 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 module according to claim 15 or 16, wherein: 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 module according to any one of claims 15 to 17, wherein: 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 module according to claim 18, wherein: The width of the fourth separation groove is smaller than the width of the second separation groove.

20. The solar cell module according to any one of claims 15 to 19, wherein: 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 module according to any one of claims 15 to 20, wherein: 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, wherein: 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, and the longitudinal portion Filling the second separation groove, with the end of the longitudinal portion 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, wherein: 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, wherein: The barrier layer is prepared by atomic layer deposition.

25. The preparation method according to any one of claims 22 to 24, wherein 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 device, wherein: 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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