Trans-perovskite solar cell and preparation method thereof

Abstract

The invention provides a trans-perovskite solar cell and a preparation method thereof. The trans-perovskite solar cell sequentially comprises a transparent conductive substrate, a hole transport layer, a modification layer, a perovskite layer, an electron transport layer and a composite transparent electrode in the thickness direction, the composite transparent electrode sequentially comprises a first transparent conductive oxide layer, a carbon nanotube layer and a second transparent conductive oxide layer in the thickness direction. The trans-perovskite solar cell is low in production cost, high in stability and high in photoelectric conversion efficiency.

Description

Technical Field

[0001] The invention belongs to the field of solar cells, and in particular relates to an inverse perovskite solar cell and a preparation method thereof. Background Art

[0002] A solar cell is a device that converts solar energy directly into electrical energy. Its core part is a photosensitive material that absorbs sunlight and generates electron-hole pairs. Trans-perovskite solar cells are a new type of solar cell, which are characterized by high photoelectric conversion efficiency and low production cost. However, the performance of trans-perovskite solar cells is affected by multiple factors, among which the performance of the counter electrode is an important influencing factor. The main function of the counter electrode is to collect and transmit electrons, and its performance directly affects the photoelectric conversion efficiency of the cell.

[0003] The existing technology uses transparent electrode materials as the counter electrode of solar cells. Commonly used transparent electrode materials include tin-doped indium oxide (ITO) and fluorine-doped tin oxide (FTO), which have improved the photoelectric conversion efficiency of perovskite solar cells to a certain extent, but there are still some problems and shortcomings. First, the cost of traditional transparent electrode materials such as ITO and FTO is relatively high, which increases the production cost of inverse perovskite solar cells. Secondly, these materials may have stability problems under certain conditions, which in turn affects the photoelectric conversion efficiency. For example, in high temperature or humid environments, it will lead to a decrease in electrode performance.

[0004] Therefore, there is an urgent need to develop a composite transparent electrode that can be used for inverse perovskite solar cells, so as to reduce production costs and improve the stability and photoelectric conversion efficiency of inverse perovskite solar cells. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention proposes an inverted perovskite solar cell comprising a composite transparent electrode, wherein the composite transparent electrode comprises a first transparent conductive oxide layer, a carbon nanotube layer and a second transparent conductive oxide layer in sequence in the thickness direction, which can reduce production costs and improve the stability and photoelectric conversion efficiency of the inverted perovskite solar cell.

[0006] Specifically, the present invention provides an inverted perovskite solar cell, which comprises, in sequence in the thickness direction, a transparent conductive substrate, a hole transport layer, a modification layer, a perovskite layer, an electron transport layer and a composite transparent electrode; the composite transparent electrode comprises, in sequence in the thickness direction, a first transparent conductive oxide layer, a carbon nanotube layer and a second transparent conductive oxide layer, and the first transparent conductive oxide layer is in contact with the electron transport layer.

[0007] In one or more embodiments, the first transparent conductive oxide layer has a thickness of 30-100 nm.

[0008] In one or more embodiments, the carbon nanotube layer has a thickness of 1-20 nm.

[0009] In one or more embodiments, the second transparent conductive oxide layer has a thickness of 30-100 nm.

[0010] In one or more embodiments, the first transparent conductive oxide is selected from one or more of indium tin oxide, indium zinc oxide, fluorine-doped tin oxide, tungsten-doped indium oxide, and cerium-doped indium oxide.

[0011] In one or more embodiments, the second transparent conductive oxide is selected from one or more of indium tin oxide, indium zinc oxide, fluorine-doped tin oxide, tungsten-doped indium oxide, and cerium-doped indium oxide.

[0012] In one or more embodiments, the transparent conductive substrate comprises a transparent substrate and a conductive coating, the transparent substrate is a flexible substrate or a rigid substrate, and the conductive coating is made of one or more selected from indium tin oxide, fluorine-doped tin oxide and indium zinc oxide.

[0013] In one or more embodiments, the transparent conductive substrate has a thickness of 100-1000 nm.

[0014] In one or more embodiments, the hole transport layer material is selected from one or more of NiOx, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid and 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, 1≤x≤2.

[0015] In one or more embodiments, the hole transport layer has a thickness of 5-100 nm.

[0016] In one or more embodiments, the modification layer material is selected from one or more of benzamidine hydroiodide, thiophenecarboxamide hydroiodide and lead iodide thiophenecarboxamide.

[0017] In one or more embodiments, the modified layer has a thickness of 1-10 nm.

[0018] In one or more embodiments, the perovskite layer material is ABX3, A is selected from methylamine cation, methylamine cation, Cs + , Rb + , butylamine cation, phenethylamine cation, fluorophenethylammonium cation, 4-fluoro-phenethylammonium cation, B is selected from one or more of Pb, Sn and Bi, and X is selected from one or more of Cl, Br, I and SCN-.

[0019] In one or more embodiments, the perovskite layer has a thickness of 200-1000 nm.

[0020] In one or more embodiments, the electron transport layer includes a C60 layer and a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline layer or a C60 layer and a SnO2 layer; preferably, the thickness of the C60 layer is 20-50nm, the thickness of the 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline layer is 6-10nm, and the thickness of the SnO2 layer is 5-30nm.

[0021] In one or more embodiments, the electron transport layer has a thickness of 25-80 nm.

[0022] In one or more embodiments, the inverse perovskite solar cell includes an encapsulation structure.

[0023] The present invention provides a method for preparing the inverse perovskite solar cell of the present invention, the method comprising the following steps:

[0024] (1) depositing a hole transport layer material on a surface of a transparent conductive substrate to obtain a hole transport layer;

[0025] (2) depositing a modification layer solution on the surface of the hole transport layer to obtain a modification layer;

[0026] (3) depositing a perovskite precursor solution on the surface of the modified layer to obtain a perovskite layer;

[0027] (4) depositing an electron transport layer material on the surface of the perovskite layer to obtain an electron transport layer;

[0028] (5) depositing a first transparent conductive oxide on the surface of the electron transport layer to obtain a first transparent conductive oxide layer; depositing carbon nanotubes on the surface of the first transparent conductive oxide layer to obtain a transparent composite electrode precursor having a carbon nanotube layer; annealing the transparent composite electrode precursor having a carbon nanotube layer to obtain a transparent composite electrode intermediate having a carbon nanotube layer; depositing a second transparent conductive oxide on the surface of the carbon nanotube layer of the transparent composite electrode intermediate to obtain a composite transparent electrode consisting of the first transparent conductive oxide layer, the carbon nanotube layer and the second transparent conductive oxide layer, thereby obtaining an inverted perovskite solar cell.

[0029] In one or more embodiments, in step (1), the hole transport layer is deposited by vacuum deposition, doctor blade coating, plasma deposition or slit coating.

[0030] In one or more embodiments, in step (2), the modification layer is deposited by vacuum deposition, blade coating or slit coating.

[0031] In one or more embodiments, in step (3), the perovskite layer is deposited by blade coating, spin coating or slit coating.

[0032] In one or more embodiments, in step (4), the electron transport layer is deposited by chemical bath method, vacuum evaporation, plasma deposition or atomic layer deposition.

[0033] In one or more embodiments, in step (2), the concentration of the modification layer solution is 0.1-5 mg / mL.

[0034] In one or more embodiments, in step (2), the solvent of the modification layer solution is selected from one or more of isopropanol, ethanol and chlorobenzene.

[0035] In one or more embodiments, in step (3), the concentration of B element in the perovskite precursor solution is 0.2-3 mol / L, and B is selected from one or more of Pb, Sn and Bi.

[0036] In one or more embodiments, in step (3), the solvent of the perovskite precursor solution is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile and 2-methoxyestradiol.

[0037] In one or more embodiments, in step (5), the first transparent conductive oxide is deposited by magnetron sputtering.

[0038] In one or more embodiments, in step (5), the temperature of the annealing treatment is 30-120°C.

[0039] In one or more embodiments, in step (5), the carbon nanotube layer is deposited by solution coating deposition, blade coating deposition, chemical vapor deposition or plasma enhanced chemical vapor deposition.

[0040] In one or more embodiments, in step (5), the second transparent conductive oxide is deposited by magnetron sputtering.

[0041] The method for preparing the inverse perovskite solar cell provided by the present invention further comprises: post-processing the composite transparent electrode prepared in step (5).

[0042] In one or more embodiments, the post-treatment method is selected from one of heat treatment, plasma treatment and chemical functionalization. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 Schematic diagram of the composite transparent electrode structure according to some embodiments of the present invention.

[0044] Figure 2 Schematic diagram of the structure of an inverted perovskite solar cell according to some embodiments of the present invention. DETAILED DESCRIPTION

[0045] In order to enable those skilled in the art to understand the characteristics and effects of the present invention, the following is a general description and definition of the terms and expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used in the text are the common meanings understood by those skilled in the art for the present invention. In the event of a conflict, the definition in this specification shall prevail.

[0046] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0047] Herein, “comprising”, “including”, “containing” and similar terms encompass the meanings of “consisting essentially of” and “consisting of”. For example, when “A comprises B and C” is disclosed herein, “A consists essentially of B and C” and “A consists of B and C” should be deemed to be disclosed herein.

[0048] In this article, all features such as values, quantities, contents and concentrations defined in the form of numerical ranges or percentage ranges are only for brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have included and specifically disclosed all possible secondary ranges and individual values ​​within the range (including integers and fractions).

[0049] In this document, unless otherwise specified, percentage refers to mass percentage and ratio refers to mass ratio.

[0050] Herein, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all substitutes, improvements and equivalents of the methods and materials described in the present invention can be included in the scope limited by the claims.

[0051] In this document, in order to make the description concise, not all possible combinations of various technical features in various embodiments or examples are described. Therefore, as long as there is no contradiction in the combination of these technical features, the various technical features in various embodiments or examples can be combined arbitrarily, and all possible combinations should be considered to be within the scope of this specification.

[0052] The present invention provides an inverted perovskite solar cell, which comprises a transparent conductive substrate, a hole transport layer, a modification layer, a perovskite layer, an electron transport layer and a composite transparent electrode in sequence in the thickness direction; the composite transparent electrode comprises a first transparent conductive oxide layer, a carbon nanotube layer and a second transparent conductive oxide layer in sequence in the thickness direction, and the first transparent conductive oxide layer is in contact with the electron transport layer.

[0053] In the present invention, carbon nanotubes are a new type of nanomaterial with relatively low cost and excellent electrical and mechanical properties. By introducing carbon nanotubes into electrodes and applying them to inverse perovskite solar cells, production costs can be reduced, electrode stability can be improved, and the transmittance and conductivity of the composite transparent electrode can be improved, thereby improving the photoelectric conversion efficiency of the battery.

[0054] In the present invention, by preparing a TCO / carbon nanotube / TCO composite transparent electrode, the transmittance and conductivity of the electrode can be simultaneously improved, thereby improving the filling factor and photoelectric conversion efficiency of the inverse perovskite solar cell.

[0055] In the present invention, the thickness of the first transparent conductive oxide layer can be 30-100 nm, for example, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm. The present invention controls the thickness of the first transparent conductive oxide layer within the above range, which can improve the light transmittance and conductivity of the electrode, thereby improving the filling factor and photoelectric conversion efficiency of the inverse perovskite solar cell.

[0056] In the present invention, the thickness of the carbon nanotube layer can be 1-20nm, for example, 2nm, 4nm, 6nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm. The present invention controls the thickness of the carbon nanotube layer within the above range, which can improve the light transmittance and conductivity of the electrode, thereby improving the filling factor and photoelectric conversion efficiency of the inverse perovskite solar cell.

[0057] In the present invention, the thickness of the second transparent conductive oxide layer can be 30-100 nm, for example, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm. The present invention controls the thickness of the second transparent conductive oxide layer within the above range, which can improve the light transmittance and conductivity of the electrode, thereby improving the filling factor and photoelectric conversion efficiency of the inverse perovskite solar cell.

[0058] In the present invention, the first transparent conductive oxide (TCO) may be one or more selected from indium tin oxide (ITO), indium zinc oxide (IZO), fluorine-doped tin oxide (FTO), tungsten-doped indium oxide (IWO) and cerium-doped indium oxide (ICO).

[0059] In the present invention, the second transparent conductive oxide may be one or more selected from indium tin oxide, indium zinc oxide, fluorine-doped tin oxide, tungsten-doped indium oxide, and cerium-doped indium oxide.

[0060] In the present invention, the transparent conductive substrate includes a transparent substrate and a conductive coating. The transparent substrate can be a flexible substrate or a rigid substrate. In some embodiments, the flexible substrate can be a flexible polyimide, and in some embodiments, the rigid substrate can be a glass substrate. The material of the conductive coating can be one or more selected from indium tin oxide (ITO), fluorine-doped tin oxide and indium zinc oxide.

[0061] In the present invention, the thickness of the transparent conductive substrate may be 100-1000 nm, for example, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm.

[0062] In the present invention, the hole transport layer material can be one or more selected from NiOx, [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2-PACz), [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid and 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, and 1≤x≤2.

[0063] In the present invention, the thickness of the hole transport layer can be 5-100 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm.

[0064] In the present invention, the material of the modification layer can be one or more selected from benzamidine hydroiodide, thiophenecarboxamide hydroiodide and lead iodide thiophenecarboxamide.

[0065] In the present invention, the thickness of the modification layer may be 1-10 nm, for example, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, and 10 nm.

[0066] In the present invention, the material of the perovskite layer can be ABX3, and A can be selected from methylamine cation (MA + ), FA + ), Cs + , Rb + , butylamine cation (BA + ), phenylethylamine cation (PEA + ), fluorophenethylammonium cation (F-PEA +), 4-fluoro-phenylethylammonium cation (4F-PEA + ), B may be one or more selected from Pb, Sn and Bi, and X may be one or more selected from Cl, Br, I and SCN-.

[0067] In the present invention, the thickness of the perovskite layer may be 200-1000 nm, for example, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm.

[0068] In the present invention, the electron transport layer may include a C60 layer and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). Preferably, the thickness of the C60 layer may be 20-50 nm, such as 10 nm, 20 nm, 30 nm, 40 nm, 50 nm. The thickness of the 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline layer may be 6-10 nm, such as 6 nm, 7 nm, 8 nm, 9 nm, 10 nm. The thickness of the SnO2 layer may be 5-30 nm, such as 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm.

[0069] In the present invention, the thickness of the electron transport layer can be 25-80 nm, for example, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm.

[0070] In the present invention, the inverse perovskite solar cell may include a packaging structure.

[0071] The present invention provides a method for preparing an inverse perovskite solar cell of the present invention, the method comprising the following steps:

[0072] (1) depositing a hole transport layer material on a surface of a transparent conductive substrate to obtain a hole transport layer;

[0073] (2) depositing a modification layer solution on the surface of the hole transport layer to obtain a modification layer;

[0074] (3) depositing a perovskite precursor solution on the surface of the modified layer to obtain a perovskite layer;

[0075] (4) depositing an electron transport layer material on the surface of the perovskite layer to obtain an electron transport layer;

[0076] (5) depositing a first transparent conductive oxide on the surface of the electron transport layer to obtain a first transparent conductive oxide layer; depositing carbon nanotubes on the surface of the first transparent conductive oxide layer to obtain a transparent composite electrode precursor having a carbon nanotube layer; annealing the transparent composite electrode precursor having a carbon nanotube layer to obtain a transparent composite electrode intermediate having a carbon nanotube layer; depositing a second transparent conductive oxide on the surface of the carbon nanotube layer of the transparent composite electrode intermediate to obtain a composite transparent electrode consisting of the first transparent conductive oxide layer, the carbon nanotube layer and the second transparent conductive oxide layer, and simultaneously obtaining an inverse perovskite solar cell.

[0077] In step (1), the hole transport layer can be deposited by vacuum deposition, doctor blade coating, plasma deposition or slit coating.

[0078] In step (2), the modification layer can be deposited by vacuum deposition, blade coating or slit coating.

[0079] In step (3), the deposition method of the perovskite layer can be blade coating, spin coating or slit coating.

[0080] In step (4), the electron transport layer can be deposited by chemical bath method, vacuum evaporation, plasma deposition or atomic layer deposition.

[0081] In step (2), the concentration of the modification layer solution can be 0.1-5 mg / mL, for example 0.5 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, 5 mg / mL.

[0082] In step (2), the solvent of the modification layer solution may be one or more selected from isopropanol, ethanol or chlorobenzene.

[0083] In step (3), the concentration of element B in the perovskite precursor solution can be 0.2-3 mol / L, for example, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, and B is selected from one or more of Pb, Sn and Bi.

[0084] In step (3), the solvent of the perovskite precursor solution may be one or more selected from N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), acetonitrile and 2-methoxyestradiol (2-Me).

[0085] In step (5), the first transparent conductive oxide may be deposited by magnetron sputtering.

[0086] In step (5), the temperature of the annealing treatment can be 30-120°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C.

[0087] In step (5), the carbon nanotube layer can be deposited by solution coating deposition, blade coating deposition, chemical vapor deposition or plasma enhanced chemical vapor deposition.

[0088] In step (5), the second transparent conductive oxide may be deposited by magnetron sputtering.

[0089] The preparation method of the present invention further comprises: post-processing the composite transparent electrode obtained in step (5); preferably, the post-processing method can be one selected from heat treatment, plasma treatment and chemical functionalization.

[0090] The present invention also provides a composite transparent electrode, which comprises a first transparent conductive oxide layer, a carbon nanotube layer and a second transparent conductive oxide layer in the thickness direction. The materials, thicknesses and preparation methods of the first transparent conductive oxide layer, the carbon nanotube layer and the second transparent conductive oxide layer can be as described in any of the above embodiments.

[0091] The present invention also provides application of the composite transparent electrode of the present invention in solar cells, displays, touch screens and optoelectronic devices.

[0092] Compared with the prior art, the present invention has the following beneficial effects:

[0093] (1) Cost reduction: The present invention uses a TCO / carbon nanotube / TCO composite transparent electrode as the counter electrode of the inverse perovskite solar cell. The cost of carbon nanotubes is lower than that of TCO. Therefore, compared with the traditional TCO electrode, the cost can be effectively reduced;

[0094] (2) Improved stability: The TCO / carbon nanotube / TCO composite transparent electrode of the present invention has good stability, and the electrode performance will not decrease even in high temperature or humid environment;

[0095] (3) Improving photoelectric conversion efficiency: The present invention can effectively improve the photoelectric conversion efficiency of the perovskite component by introducing a TCO / carbon nanotube / TCO composite transparent electrode.

[0096] The present invention will be described below in the form of specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise stated, conventional methods, reagents and materials in the art. The raw material compounds in the examples can all be purchased through commercial routes.

[0097] The NiOx in the examples and comparative examples of the present invention was purchased from Zhongchengda.

[0098] Example 1

[0099] This example was prepared according to the following steps Figure 2 An inverted perovskite solar cell shown:

[0100] (1) NiOx was deposited on the surface of a transparent ITO conductive substrate with a thickness of 100 nm (wherein the transparent substrate was a glass substrate and the conductive coating was ITO) by plasma deposition to obtain a hole transport layer with a thickness of 30 nm;

[0101] (2) depositing a modification layer solution on the surface of the hole transport layer by a doctor blade coating method to obtain a modification layer with a thickness of 10 nm, wherein the solute of the modification layer solution is benzamidine hydroiodide, the solvent is isopropanol, and the concentration is 1 mg / mL;

[0102] (3) A perovskite precursor solution was deposited on the surface of the modified layer by a doctor blade coating method to obtain a perovskite layer with a thickness of 500 nm, wherein FAI, CsI and PbI2 were weighed in a molar ratio of 0.9:0.1:1, and a mixed solution of DMF and DMSO in a volume ratio of 4:1 was added thereto, and the mixture was shaken for 2 h until the solute was completely dissolved to obtain a perovskite precursor solution. The solute of the perovskite precursor solution was the theoretically generated FA 0.9 Cs 0.1 PbI3, the solvent is a mixture of DMF and DMSO with a volume ratio of 4:1, and the concentration of Pb ions in the perovskite precursor solution is 1.2 mol / L;

[0103] (4) depositing C60 and BCP on the surface of the perovskite layer in sequence by vacuum evaporation to obtain an electron transport layer with a C60 layer thickness of 40 nm and a BCP layer thickness of 8 nm;

[0104] (5) ITO is deposited on the surface of the electron transport layer by magnetron sputtering to obtain a first transparent conductive oxide with a thickness of 50 nm; carbon nanotubes are deposited on the surface of the ITO layer by scraping to obtain a carbon nanotube layer with a thickness of 20 nm; after annealing at 50° C., ITO is deposited on the surface of the carbon nanotube layer by magnetron sputtering to obtain a second transparent conductive oxide with a thickness of 50 nm. The first transparent conductive oxide layer, the carbon nanotube layer, and the second transparent conductive oxide layer constitute a composite transparent electrode, and an inverse perovskite solar cell is obtained at the same time.

[0105] Example 2

[0106] This example was prepared according to the following steps Figure 2 An inverted perovskite solar cell shown:

[0107] (1) depositing 2-PACz on the surface of a transparent ITO conductive substrate with a thickness of 100 nm (wherein the transparent substrate is a glass substrate and the conductive coating is ITO) by a scraping method to obtain a hole transport layer with a thickness of 10 nm;

[0108] (2) depositing a modification layer solution on the surface of the hole transport layer by a doctor blade coating method to obtain a modification layer with a thickness of 5 nm, wherein the solute of the modification layer solution is thiophenecarboxamide hydroiodide, the solvent is isopropanol, and the concentration is 1.5 mg / mL;

[0109] (3) A perovskite precursor solution was deposited on the surface of the modified layer by spin coating to obtain a perovskite layer with a thickness of 400 nm, wherein FAI, CsI and PbI2 were weighed in a molar ratio of 0.83:0.17:1, and a mixed solution of DMF and NMP in a volume ratio of 8:1 was added thereto, and the mixture was shaken for 2 h until the solute was completely dissolved to obtain a perovskite precursor solution. The solute of the perovskite precursor solution was the theoretically generated FA 0.83 Cs 0.17 PbI3, the solvent is a mixture of DMF and NMP with a volume ratio of 8:1, and the concentration of Pb ions in the perovskite precursor solution is 0.8 mol / L;

[0110] (4) depositing C60 on the surface of the perovskite layer by vacuum evaporation, and then depositing SnO2 on the surface of the C60 layer by atomic layer deposition to obtain an electron transport layer with a C60 layer thickness of 30 nm and a SnO2 layer thickness of 20 nm;

[0111] (5) IZO is deposited on the surface of the electron transport layer by magnetron sputtering to obtain a first transparent conductive oxide with a thickness of 30 nm; carbon nanotubes are deposited on the surface of the IZO layer by scraping to obtain a carbon nanotube layer with a thickness of 10 nm; after annealing at 50°C, IZO is deposited on the surface of the carbon nanotube layer by magnetron sputtering to obtain a second transparent conductive oxide with a thickness of 40 nm. The first transparent conductive oxide layer, the carbon nanotube layer and the second transparent conductive oxide layer form a composite transparent electrode, and an inverse perovskite solar cell is obtained at the same time.

[0112] Comparative Example 1

[0113] The only difference from Example 1 is that in step (5), 120 nm of ITO is deposited on the surface of the electron transport layer by magnetron sputtering as a transparent electrode to obtain an inverse perovskite solar cell.

[0114] (1) NiOx was deposited on the surface of a transparent ITO conductive substrate with a thickness of 100 nm (wherein the transparent substrate was a glass substrate and the conductive coating was ITO) by plasma deposition to obtain a hole transport layer with a thickness of 30 nm;

[0115] (2) depositing a modification layer solution on the surface of the hole transport layer by a doctor blade coating method to obtain a modification layer with a thickness of 10 nm, wherein the solute of the modification layer solution is benzamidine hydroiodide, the solvent is isopropanol, and the concentration is 1 mg / mL;

[0116] (3) A perovskite precursor solution was deposited on the surface of the modified layer by a doctor blade coating method to obtain a perovskite layer with a thickness of 500 nm, wherein FAI, CsI and PbI2 were weighed in a molar ratio of 0.9:0.1:1, and a mixed solution of DMF and DMSO in a volume ratio of 4:1 was added thereto, and the mixture was shaken for 2 h until the solute was completely dissolved to obtain a perovskite precursor solution. The solute of the perovskite precursor solution was the theoretically generated FA 0.9 Cs 0.1 PbI3, the solvent is a mixture of DMF and DMSO with a volume ratio of 4:1, and the concentration of Pb ions in the perovskite precursor solution is 1.2 mol / L;

[0117] (4) depositing C60 and BCP on the surface of the perovskite layer in sequence by vacuum evaporation to obtain an electron transport layer with a C60 layer thickness of 40 nm and a BCP layer thickness of 8 nm;

[0118] (5) A 120 nm thick ITO was deposited on the surface of the electron transport layer by magnetron sputtering as a transparent electrode to obtain an inverse perovskite solar cell.

[0119] Comparative Example 2

[0120] The only difference from Example 2 is that in step (5), 80 nm of IZO is deposited on the surface of the electron transport layer by magnetron sputtering as a transparent electrode to obtain an inverse perovskite solar cell.

[0121] (1) depositing 2-PACz on the surface of a transparent ITO conductive substrate with a thickness of 100 nm (wherein the transparent substrate is a glass substrate and the conductive coating is ITO) by a scraping method to obtain a hole transport layer with a thickness of 10 nm;

[0122] (2) depositing a modification layer solution on the surface of the hole transport layer by a doctor blade coating method to obtain a modification layer with a thickness of 5 nm, wherein the solute of the modification layer solution is thiophenecarboxamide hydroiodide, the solvent is isopropanol, and the concentration is 1.5 mg / mL;

[0123] (3) A perovskite precursor solution was deposited on the surface of the modified layer by spin coating to obtain a perovskite layer with a thickness of 400 nm, wherein FAI, CsI and PbI2 were weighed in a molar ratio of 0.83:0.17:1, and a mixed solution of DMF and NMP in a volume ratio of 8:1 was added thereto, and the mixture was shaken for 2 h until the solute was completely dissolved to obtain a perovskite precursor solution. The solute of the perovskite precursor solution was the theoretically generated FA0.83 Cs 0.17 PbI3, the solvent is a mixture of DMF and NMP with a volume ratio of 8:1, and the concentration of Pb ions in the perovskite precursor solution is 0.8 mol / L;

[0124] (4) depositing C60 on the surface of the perovskite layer by vacuum evaporation, and then depositing SnO2 on the surface of the C60 layer by atomic layer deposition to obtain an electron transport layer with a C60 layer thickness of 30 nm and a SnO2 layer thickness of 20 nm;

[0125] (5) An 80 nm thick IZO was deposited on the surface of the electron transport layer by magnetron sputtering as a transparent electrode to obtain an inverse perovskite solar cell.

[0126] Test Case

[0127] Performance test of inverse perovskite solar cells: at 25°C, AM 1.5G standard solar spectrum, irradiance of 1000W / m 2 Under the condition of , using a solar simulator, the voltage range is set to -0.2V-1.25V, the current output of the inverted perovskite solar cells prepared in Example 1-2 and Comparative Example 1-2 at different voltages is tested, and the corresponding current-voltage (IV) characteristic curves are plotted, wherein the cell surface area is 0.1cm 2 , the incident light power (Pin) is 100mW / cm 2 .

[0128] (1) Open circuit voltage (Voc): The voltage value corresponding to when the current is equal to zero.

[0129] (2) Short-circuit current density (Jsc): The current value when the voltage is zero is the short-circuit current (Isc), and the current per unit battery surface area is the short-circuit current density.

[0130] (3) Fill factor (FF): The ratio of the maximum output power (Pmax) of the battery to the product of the open circuit voltage and the short circuit current. The calculation formula is (Pmax / Voc*Isc), where the maximum power point is the point where the battery output power reaches its maximum value.

[0131] (4) Photoelectric conversion efficiency (PCE): Photoelectric conversion efficiency refers to the ratio of maximum output power to incident light power (Pin), and the calculation formula is (Pmax / Pin)*100%.

[0132] The open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the inverted perovskite solar cells prepared in Example 1-2 and Comparative Example 1-2 were obtained according to the IV curves.

[0133] Table 1: Open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency of the inverse perovskite solar cells prepared in Examples 1-2 and Comparative Examples 1-2

[0134] Group Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF(%) PCE(%) Example 1 1.17 24.83 82.5 22.91 Example 2 1.18 25.33 83.0 24.81 Comparative Example 1 1.13 24.16 78.1 21.32 Comparative Example 2 1.14 23.62 76.1 20.49

[0135] As can be seen from Table 1, the inverse perovskite solar cell prepared in Example 1 has higher open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency than the inverse perovskite solar cell prepared in Comparative Example 1; and the inverse perovskite solar cell prepared in Example 2 has higher open circuit voltage, short circuit current density, fill factor and photoelectric conversion efficiency than the inverse perovskite solar cell prepared in Comparative Example 2. This shows that the inverse perovskite solar cell prepared in the present invention has excellent performance.

Claims

1. An inverted perovskite solar cell, characterized in that: The inverted perovskite solar cell includes a transparent conductive substrate, a hole transport layer, a modification layer, a perovskite layer, an electron transport layer and a composite transparent electrode in sequence in the thickness direction; the composite transparent electrode includes a first transparent conductive oxide layer, a carbon nanotube layer and a second transparent conductive oxide layer in sequence in the thickness direction, and the first transparent conductive oxide layer is in contact with the electron transport layer.

2. The inverted perovskite solar cell according to claim 1, characterized in that: The inverse perovskite solar cell has one or more of the following features: The thickness of the first transparent conductive oxide layer is 30-100 nm; The thickness of the carbon nanotube layer is 1-20 nm; The thickness of the second transparent conductive oxide layer is 30-100 nm.

3. The inverted perovskite solar cell according to claim 1, characterized in that: The first transparent conductive oxide is selected from one or more of indium tin oxide, indium zinc oxide, fluorine-doped tin oxide, tungsten-doped indium oxide and cerium-doped indium oxide; and / or The second transparent conductive oxide is selected from one or more of indium tin oxide, indium zinc oxide, fluorine-doped tin oxide, tungsten-doped indium oxide and cerium-doped indium oxide.

4. A method for preparing the inverse perovskite solar cell according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: (1) depositing a hole transport layer material on a surface of a transparent conductive substrate to obtain a hole transport layer; (2) depositing a modification layer solution on the surface of the hole transport layer to obtain a modification layer; (3) depositing a perovskite precursor solution on the surface of the modified layer to obtain a perovskite layer; (4) depositing an electron transport layer material on the surface of the perovskite layer to obtain an electron transport layer; (5) depositing a first transparent conductive oxide on the surface of the electron transport layer to obtain a first transparent conductive oxide layer; depositing carbon nanotubes on the surface of the first transparent conductive oxide layer to obtain a transparent composite electrode precursor having a carbon nanotube layer; annealing the transparent composite electrode precursor having a carbon nanotube layer to obtain a transparent composite electrode intermediate having a carbon nanotube layer; depositing a second transparent conductive oxide on the surface of the carbon nanotube layer of the transparent composite electrode intermediate to obtain a composite transparent electrode consisting of the first transparent conductive oxide layer, the carbon nanotube layer and the second transparent conductive oxide layer, thereby obtaining an inverted perovskite solar cell.

5. The method according to claim 4, characterized in that In step (5), the first transparent conductive oxide is deposited by magnetron sputtering.

6. The method according to claim 4, characterized in that In step (5), the temperature of the annealing treatment is 30-120°C.

7. The method according to claim 4, characterized in that In step (5), the carbon nanotube layer is deposited by solution coating deposition, blade coating deposition, chemical vapor deposition or plasma enhanced chemical vapor deposition.

8. The method according to claim 4, characterized in that In step (5), the second transparent conductive oxide is deposited by magnetron sputtering.

9. The method according to claim 4, characterized in that The method further comprises: post-processing the composite transparent electrode obtained in step (5).

10. The method according to claim 9, characterized in that The post-treatment method is selected from one of heat treatment, plasma treatment and chemical functionalization.

Images