Perovskite solar cell and method of manufacturing the same

Abstract

The application provides a perovskite solar cell and a preparation method thereof. The perovskite solar cell comprises a transparent conductive film, a hole transport layer, a perovskite absorption layer, an electron transport layer, an indium tin oxide layer and a back electrode which are sequentially arranged. The perovskite solar cell has good stability and high photoelectric conversion efficiency.

Description

Technical Field

[0001] This invention belongs to the field of solar cell technology, specifically relating to a perovskite solar cell and its preparation method. Background Technology

[0002] As a crucial member of the renewable energy family, the development and use of solar energy is of paramount importance. Solar energy boasts advantages such as abundant reserves, easy access, and zero environmental pollution, thus its development and use have garnered widespread attention worldwide.

[0003] Perovskite solar cells are one type of solar cell among many, and a third-generation solar cell developed in recent years, characterized by high conversion efficiency and low manufacturing cost. Achieving large-scale mass production of perovskite solar photovoltaic modules will be one of the important ways to achieve grid parity for photovoltaic power. Currently, perovskite solar cells still face some unavoidable problems in their industrialization process, such as improving module stability and how to achieve large-area uniform fabrication of the various film layers in the cell. In the industrial production of thin-film batteries, magnetron sputtering is commonly used to prepare the various film layers because it is stable and allows for large-area film fabrication. However, the sputtering process generates high-energy particles that strongly bombard the substrate to be coated, which has a significant impact on the perovskite layer. Furthermore, since the compounds in the perovskite layer are mainly bonded by ionic bonds, they are easily decomposed under ion bombardment, directly damaging the perovskite absorber layer and thus reducing the efficiency and stability of the device.

[0004] Therefore, existing perovskite solar cells need improvement. Summary of the Invention

[0005] This invention aims to at least partially solve one of the technical problems in related technologies. Therefore, one object of this invention is to provide a perovskite solar cell and a method for fabricating the same, which exhibits good stability and high photoelectric conversion efficiency.

[0006] In one aspect of the present invention, a perovskite solar cell is provided. According to an embodiment of the present invention, the perovskite solar cell includes a transparent conductive film, a hole transport layer, a perovskite absorber layer, an electron transport layer, an indium tin oxide layer, and a back electrode arranged sequentially.

[0007] According to an embodiment of the present invention, the perovskite solar cell includes a transparent conductive film, a hole transport layer, a perovskite absorber layer, an electron transport layer, an indium tin oxide (ITO) layer, and a back electrode, arranged sequentially. Specifically, an ITO layer is added between the electron transport layer and the back electrode. This ITO layer can block high-energy particles during the vacuum sputtering fabrication of the back electrode, reducing the disruption of ionic bonds in the perovskite absorber layer and the damage to the electron transport layer caused by high-energy particles, thereby improving stability. Simultaneously, the ITO layer formed on the electron transport layer can protect both the electron transport layer and the perovskite absorber layer during the vacuum laser scribing process, thereby improving device efficiency. Therefore, the perovskite solar cell exhibits good stability and high photoelectric conversion efficiency.

[0008] In addition, the perovskite solar cell according to the above embodiments of the present invention may also have the following additional technical features:

[0009] According to an embodiment of the present invention, the hole transport layer has a thickness of 5-50 nm, the perovskite absorber layer has a thickness of 100-1000 nm, the electron transport layer has a thickness of 5-50 nm, and the back electrode has a thickness of 50-300 nm.

[0010] According to an embodiment of the present invention, the mass percentage of tin oxide in the indium tin oxide layer is 3% to 10%. This improves the stability and photoelectric conversion efficiency of the perovskite solar cell.

[0011] According to an embodiment of the present invention, the thickness of the indium tin oxide layer is 10 nm to 200 nm. This improves the stability and photoelectric conversion efficiency of the perovskite solar cell.

[0012] In another aspect, the present invention provides a method for preparing perovskite solar cells. According to an embodiment of the present invention, the method includes:

[0013] (1) A hole transport layer, a perovskite absorption layer and an electron transport layer are sequentially formed on a transparent conductive film glass substrate;

[0014] (2) An indium tin oxide layer is formed on the electron transport layer by electron beam deposition;

[0015] (3) A back electrode is formed on the indium tin oxide layer.

[0016] Therefore, the method of the present invention can be used to prepare the above-mentioned perovskite solar cell with good stability and high photoelectric conversion efficiency. At the same time, the formation of an indium tin oxide layer on the electron transport layer by electron beam deposition can reduce the energy of ITO particles during the film formation process, thereby reducing the damage to the electron transport layer and the perovskite absorption layer.

[0017] In addition, the method for preparing perovskite solar cells according to the above embodiments of the present invention may also have the following additional technical features:

[0018] According to an embodiment of the present invention, the electron beam deposition method includes: placing the sample obtained in step (1), comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, on a rotating platform; using indium tin oxide (ITO) as a precursor material, the ITO sublimates under the action of an electron beam emitted by an electron gun, thereby forming an ITO layer on the electron transport layer of the sample. This improves the stability and photoelectric conversion efficiency of the perovskite solar cell.

[0019] According to an embodiment of the present invention, the rotational speed of the rotating platform is 0–20 r / min, and the deposition rate is… The temperature inside the deposition chamber is 50–300℃. This improves the stability and photoelectric conversion efficiency of perovskite solar cells.

[0020] According to an embodiment of the present invention, the electron beam deposition method further includes ionizing the process gas using an auxiliary electron beam ion source device, such that the ionized ions are doped into the indium tin oxide layer. This can improve the photoelectric conversion efficiency of the perovskite solar cell.

[0021] According to an embodiment of the present invention, the flow rate of the process gas is 3–50 sccm. This improves the photoelectric conversion efficiency of the perovskite solar cell.

[0022] According to embodiments of the present invention, the process gas includes at least one of argon, nitrogen, oxygen, and an argon-oxygen mixture. This can improve the photoelectric conversion efficiency of perovskite solar cells.

[0023] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0024] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0025] Figure 1 This is a schematic diagram of the perovskite solar cell structure according to an embodiment of the present invention;

[0026] Figure 2 This is a schematic flowchart of a method for preparing perovskite solar cells according to an embodiment of the present invention;

[0027] Figure 3 This is a structural diagram of the equipment used to prepare the indium tin oxide layer in a perovskite solar cell according to an embodiment of the present invention;

[0028] Figure 4 The graph shows the electrical performance test results of the perovskite solar cell in Comparative Example 1.

[0029] Figure 5 The graph shows the electrical performance test results of the perovskite solar cell in Comparative Example 2.

[0030] Figure 6 The graph shows the electrical performance test results of the perovskite solar cell in Comparative Example 3.

[0031] Figure 7 This is a graph showing the electrical performance test results of the perovskite solar cell in Example 1;

[0032] Figure 8 This is a graph showing the electrical performance test results of the perovskite solar cell in Example 2;

[0033] Figure 9 This is a graph showing the electrical performance test results of the perovskite solar cell in Example 3;

[0034] Figure 10 This is a graph showing the electrical performance test results of the perovskite solar cell in Example 4;

[0035] Figure 11 This is a graph showing the electrical performance test results of the perovskite solar cell in Example 5;

[0036] Figure 12 These are the light transmittance test results of the indium tin oxide layers in Examples 6-10 and Comparative Examples 4-5. Detailed Implementation

[0037] The embodiments of the present invention are described in detail below, and are intended to explain the present invention, but should not be construed as limiting the present invention.

[0038] In one aspect of the invention, a perovskite solar cell is provided, according to an embodiment of the invention, with reference to... Figure 1 The perovskite solar cell includes a transparent conductive film 100, a hole transport layer 200, a perovskite absorber layer 300, an electron transport layer 400, an indium tin oxide layer 500, and a back electrode 600 arranged sequentially.

[0039] It should be noted that the transparent conductive film 100, hole transport layer 200, perovskite absorber layer 300, electron transport layer 400, and back electrode 600 are all conventional components in the field of perovskite solar cells. For example, the transparent conductive film 100 includes, but is not limited to, fluorine-doped tin oxide conductive glass or tin-doped indium oxide conductive glass; the hole transport layer 200 includes, but is not limited to, titanium dioxide, molybdenum trioxide, fullerene, cuprous oxide, nickel oxide, vanadium pentoxide, tin dioxide, P3HT, PTAA, zinc oxide, and PCBM. At least one of the following: the electron transport layer 400 includes, but is not limited to, at least one of cuprous iodide, cuprous oxide, nickel oxide, vanadium pentoxide, molybdenum trioxide, titanium dioxide, tin dioxide, zinc oxide, Spiro-OMeTAD, P3HT, PTAA, PEDOT:PSS, fullerene, and PCBM; the back electrode 600 includes, but is not limited to, at least one of copper electrode, silver electrode, aluminum electrode, gold electrode, chromium electrode, molybdenum electrode, tin-doped indium oxide transparent back electrode, fluorine-doped tin oxide transparent back electrode, zinc oxide transparent back electrode, and transparent electrode sandwich metal electrode.

[0040] Meanwhile, those skilled in the art can select the thickness of the transparent conductive film 100, hole transport layer 200, perovskite absorber layer 300, electron transport layer 400 and back electrode 600 according to actual needs. For example, the thickness of hole transport layer 200 is 5-50 nm, the thickness of perovskite absorber layer 300 is 100-1000 nm, the thickness of electron transport layer 400 is 5-50 nm, and the thickness of back electrode 600 is 50-300 nm.

[0041] Compared to existing technologies, the perovskite solar cell of this application adds an indium tin oxide (ITO) layer 500 between the electron transport layer 400 and the back electrode 600. This ITO layer 500 can block high-energy particles during the vacuum sputtering fabrication of the back electrode 600, reducing the damage to the ionic bonds in the perovskite absorber layer 300 and the electron transport layer 400 caused by high-energy particles, thereby improving stability. Simultaneously, the ITO layer 500 formed on the electron transport layer 400 can protect both the electron transport layer 400 and the perovskite absorber layer 300 during the vacuum laser scribing process, thus improving device efficiency. Therefore, this perovskite solar cell exhibits better stability and higher photoelectric conversion efficiency.

[0042] Furthermore, the thickness of the aforementioned indium tin oxide layer 500 is 10 nm to 200 nm. The inventors discovered that if the thickness of the indium tin oxide layer 500 is less than 10 nm, the intended protection of the electron transport layer 400 and the perovskite absorber layer 300 cannot be achieved. Subsequent vacuum breaking and sputtering will cause a decrease in device efficiency. If the thickness of the indium tin oxide layer 500 is greater than 200 nm, the excessively thick indium tin oxide layer 500 will lead to an increase in the series resistance Rs of the cell, thereby reducing the cell fill factor and efficiency. It also increases material loss and prolongs the process fabrication time. Therefore, this application uses an indium tin oxide layer 500 with a thickness of 10 nm to 200 nm as a protective layer between the electron transport layer 400 and the back electrode 600, which can improve the stability and photoelectric conversion efficiency of the perovskite solar cell.

[0043] Furthermore, the mass percentage of tin oxide in the indium tin oxide layer 500 is 3% to 10%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10%. The inventors have found that if the mass percentage of tin oxide in the indium tin oxide layer 500 is less than 3%, the resistivity of the prepared indium tin oxide layer 500 is relatively high, leading to an increase in the series resistance Rs of the cell, thereby reducing the cell fill factor and efficiency. If the mass percentage of tin oxide in the indium tin oxide layer 500 is greater than 10%, similar negative effects occur as when the mass percentage is less than 3%. Therefore, this application uses an indium tin oxide layer 500 with a tin oxide mass percentage of 3% to 10%, which can improve the stability and photoelectric conversion efficiency of perovskite solar cells. Preferably, the mass percentage of tin oxide in the indium tin oxide layer 500 is 5%.

[0044] In another aspect, the present invention provides a method for preparing the above-described perovskite solar cell, according to an embodiment of the present invention, referring to... Figure 2 The method includes:

[0045] S100: A hole transport layer, a perovskite absorption layer, and an electron transport layer are sequentially formed on a transparent conductive glass substrate.

[0046] In this step, the methods for sequentially forming the hole transport layer, the perovskite absorption layer, and the electron transport layer on the transparent conductive film glass substrate are all conventional methods in the art. Those skilled in the art can choose according to actual needs. For example, the methods for preparing the hole transport layer include, but are not limited to, at least one of sputtering, evaporation, chemical bath deposition, and precursor solution spin coating; the methods for preparing the perovskite absorption layer include, but are not limited to, at least one of spin coating, blade coating, screen printing, spray pyrolysis, and slot coating; and the methods for preparing the electron transport layer include, but are not limited to, at least one of evaporation, sputtering, and precursor solution spin coating.

[0047] S200: An indium tin oxide layer is formed on the electron transport layer using electron beam deposition.

[0048] In this step, an indium tin oxide (ITO) layer is formed on the electron transport layer using electron beam deposition. This ITO layer acts as a barrier against high-energy particles during the subsequent vacuum sputtering process for fabricating the back electrode, reducing the damage caused by high-energy particles to the ionic bonds in the perovskite absorber layer and the electron transport layer, thereby improving stability. Simultaneously, the ITO layer on the electron transport layer protects both the electron transport layer and the perovskite absorber layer during the vacuum laser scribing process, thus improving device efficiency. Furthermore, forming the ITO layer on the electron transport layer using electron beam deposition reduces the energy of ITO particles during film formation, further minimizing damage to the electron transport layer and the perovskite absorber layer. Therefore, a perovskite solar cell with good stability and high photoelectric conversion efficiency can be fabricated.

[0049] Furthermore, the step of forming an indium tin oxide layer on the electron transport layer using electron beam deposition may include: placing the sample obtained in S100, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, on a rotating platform; using indium tin oxide as a precursor material, the indium tin oxide sublimates under the action of an electron beam emitted by an electron gun, thereby forming an indium tin oxide layer on the electron transport layer, for example... Figure 3 As shown, the rotating platform 2 is located at the top of the deposition chamber 1, and indium tin oxide is placed in the crucible 3, which is located directly below the rotating platform 2.

[0050] According to one embodiment of the present invention, the rotational speed of the rotating platform 2 is 0-20 r / min, and the deposition rate is... The chamber temperature during the deposition process is 50–300°C. This allows for the deposition of a uniformly thick indium tin oxide layer on the electron transport layer. Furthermore, a film thickness gauge can be installed during the deposition process to monitor the deposition rate and the thickness of the deposited film.

[0051] According to another embodiment of the present invention, in order to improve the conductivity of the obtained indium tin oxide layer, this step further includes ionizing a process gas including at least one of argon, nitrogen, oxygen, and an argon-oxygen mixture using an auxiliary electron beam ionization source, such that the ionized ions are doped into the indium tin oxide layer, wherein the flow rate of the process gas is 3-50 sccm. Specifically, when gas ions enter the indium tin oxide layer, the concentration of charge carriers in the film layer increases, thereby improving the conductivity of the indium tin oxide layer. For example, Figure 3As shown, an ion source device 4 is arranged on the side wall of the deposition chamber. An ion source auxiliary gas inlet pipe 5 and a process gas inlet pipe are also provided. One end of the ion source auxiliary gas inlet pipe 5 is connected to the ion source device 4, and the other end is connected to the process gas inlet pipe. Process gas is introduced through the process gas inlet pipe and then enters the ion source device 4 through the ion source auxiliary gas inlet pipe 5 to ionize the supplied process gas molecules.

[0052] Specifically, the obtained sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, is placed on a rotating platform 2. Process gas is first introduced into the deposition chamber 1 through the ion source-assisted gas inlet pipe 5. After the gas pressure in the deposition chamber 1 stabilizes, the ion source device 4 is turned on, and then the electron beam power supply is activated to begin depositing the indium tin oxide layer. The electron transport layer can also be... Figure 3 The electron transport layer and the indium tin oxide layer are deposited in the same equipment, thereby improving the yield.

[0053] S300: Back electrode formed on indium tin oxide layer

[0054] In this step, the method for fabricating the back electrode on the indium tin oxide layer is a conventional method in the field of perovskite solar cells. Those skilled in the art can choose according to the actual situation, for example, using magnetron sputtering. According to one embodiment of the present invention, after the indium tin oxide layer is fabricated, the sample needs to be removed by breaking the vacuum and laser scribing is performed. After scribing, the back electrode is then fabricated on the indium tin oxide layer by magnetron sputtering.

[0055] Therefore, the method of this invention can be used to prepare the perovskite solar cell with good stability and high photoelectric conversion efficiency. It should be noted that the features and advantages described above for perovskite solar cells also apply to this method for preparing perovskite solar cells, and will not be repeated here.

[0056] The present invention will now be described with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0057] Comparative Example 1

[0058] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer using spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60The electron transport layer is 20 nm thick, and finally, an ITO / Cu / ITO sandwich back electrode is formed on the electron transport layer by magnetron sputtering. The back electrode is 100 nm thick, thus obtaining a perovskite solar cell.

[0059] Comparative Example 2

[0060] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide conductive glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer by spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60 / SnO2), with an electron transport layer thickness of 20nm.

[0061] The indium tin oxide (ITO) layer was deposited on the electron transport layer using electron beam deposition. The prepared sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, was placed on a rotating platform. Using ITO as a precursor material, the ITO sublimated under the influence of an electron beam emitted from an electron gun, thus forming the ITO layer on the electron transport layer. The rotation speed of the rotating platform was 10 r / min, and the deposition rate was [missing information]. The deposition chamber temperature was 50℃, and the thickness of the obtained indium tin oxide layer was 230nm. The mass ratio of tin oxide in the indium tin oxide layer was 2%. Finally, ITO / Cu / ITO sandwich back electrode was prepared by magnetron sputtering, and the thickness of the back electrode was 100nm, thus obtaining a perovskite solar cell.

[0062] Comparative Example 3

[0063] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide conductive glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer by spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60 / SnO2), with an electron transport layer thickness of 20nm.

[0064] The indium tin oxide (ITO) layer was deposited on the electron transport layer using electron beam deposition. The prepared sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, was placed on a rotating platform. Using ITO as a precursor material, the ITO sublimated under the influence of an electron beam emitted from an electron gun, thus forming the ITO layer on the electron transport layer. The rotation speed of the rotating platform was 10 r / min, and the deposition rate was [missing information]. The deposition chamber temperature was 50℃, and the thickness of the obtained indium tin oxide layer was 8nm. The mass ratio of tin oxide in the indium tin oxide layer was 12%. Finally, ITO / Cu / ITO sandwich back electrode was prepared by magnetron sputtering, and the thickness of the back electrode was 100nm, thus obtaining a perovskite solar cell.

[0065] Comparative Example 4

[0066] The difference between Comparative Example 4 and Comparative Example 2 in the preparation of perovskite solar cells is that: an indium tin oxide layer is deposited on the electron transport layer by electron beam deposition, the thickness of the obtained indium tin oxide layer is 80 nm, and the mass ratio of tin oxide in the indium tin oxide layer is 2%.

[0067] Comparative Example 5

[0068] The difference between Comparative Example 5 and Comparative Example 3 in the preparation of perovskite solar cells is that: an indium tin oxide layer is deposited on the electron transport layer by electron beam deposition, the thickness of the obtained indium tin oxide layer is 80 nm, and the mass ratio of tin oxide in the indium tin oxide layer is 12%.

[0069] Example 1

[0070] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide conductive glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer by spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60 / SnO2), with an electron transport layer thickness of 20nm.

[0071] The indium tin oxide (ITO) layer was deposited on the electron transport layer using electron beam deposition. The prepared sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, was placed on a rotating platform. Using ITO as a precursor material, the ITO sublimated under the influence of an electron beam emitted from an electron gun, thus forming the ITO layer on the electron transport layer. The rotation speed of the rotating platform was 10 r / min, and the deposition rate was [missing information]. The deposition chamber temperature was 50℃, and the thickness of the obtained indium tin oxide layer was 40nm. The mass ratio of tin oxide in the indium tin oxide layer was 10%. Finally, ITO / Cu / ITO sandwich back electrode was prepared by magnetron sputtering, and the thickness of the back electrode was 100nm, thus obtaining a perovskite solar cell.

[0072] Example 2

[0073] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide conductive glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer by spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60 / SnO2), with an electron transport layer thickness of 20nm.

[0074] The indium tin oxide (ITO) layer was deposited on the electron transport layer using electron beam deposition. The prepared sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, was placed on a rotating platform. Using ITO as a precursor material, the ITO sublimated under the influence of an electron beam emitted from an electron gun, thus forming the ITO layer on the electron transport layer. The rotation speed of the rotating platform was 10 r / min, and the deposition rate was [missing information]. The deposition chamber temperature was 50℃, and the thickness of the obtained indium tin oxide layer was 200nm. The mass ratio of tin oxide in the indium tin oxide layer was 3%. Finally, ITO / Cu / ITO sandwich back electrode was prepared by magnetron sputtering, and the thickness of the back electrode was 100nm, thus obtaining a perovskite solar cell.

[0075] Example 3

[0076] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide conductive glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer by spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60 / SnO2), with an electron transport layer thickness of 20nm.

[0077] The indium tin oxide (ITO) layer was deposited on the electron transport layer using electron beam deposition. The prepared sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, was placed on a rotating platform. Using ITO as a precursor material, the ITO sublimated under the influence of an electron beam emitted from an electron gun, thus forming the ITO layer on the electron transport layer. The rotation speed of the rotating platform was 10 r / min, and the deposition rate was [missing information]. The deposition chamber temperature was 50℃, and the thickness of the obtained indium tin oxide layer was 100nm. The mass ratio of tin oxide in the indium tin oxide layer was 5%. Finally, ITO / Cu / ITO sandwich back electrode was prepared by magnetron sputtering, and the thickness of the back electrode was 100nm, thus obtaining a perovskite solar cell.

[0078] Example 4

[0079] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide conductive glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer by spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60 / SnO2), with an electron transport layer thickness of 20nm.

[0080] The indium tin oxide (ITO) layer was deposited on the electron transport layer using electron beam deposition. The prepared sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, was placed on a rotating platform. Using ITO as a precursor material, the ITO sublimated under the influence of an electron beam emitted from an electron gun, thus forming the ITO layer on the electron transport layer. The rotation speed of the rotating platform was 10 r / min, and the deposition rate was [missing information]. The deposition chamber temperature was 50℃, and the thickness of the obtained indium tin oxide layer was 10nm. The mass ratio of tin oxide in the indium tin oxide layer was 8%. Finally, ITO / Cu / ITO sandwich back electrode was prepared by magnetron sputtering, and the thickness of the back electrode was 100nm, thus obtaining a perovskite solar cell.

[0081] Example 5

[0082] First, nickel oxide as a hole transport layer with a thickness of 15 nm was deposited on a fluorine-doped tin oxide conductive glass substrate using magnetron sputtering. Then, a perovskite absorber layer with a thickness of 500 nm was formed on the hole transport layer by spin coating. Finally, an electron transport layer (C) was deposited on the perovskite absorber layer using electron beam deposition. 60 / SnO2), with an electron transport layer thickness of 20nm.

[0083] The indium tin oxide (ITO) layer was deposited on the electron transport layer using electron beam deposition. The prepared sample, comprising a transparent conductive film, a hole transport layer, a perovskite absorber layer, and an electron transport layer, was placed on a rotating platform. Using ITO as a precursor material, the ITO sublimated under the influence of an electron beam emitted from an electron gun, thus forming the ITO layer on the electron transport layer. The rotation speed of the rotating platform was 10 r / min, and the deposition rate was [missing information]. The deposition temperature was 50℃. During the deposition of the indium tin oxide layer, an auxiliary electron beam ion source was used to ionize the process gas O2 / Ar mixture, so that the ionized ions were doped into the indium tin oxide layer. The process gas flow rate was 10 Sccm, and the thickness of the obtained indium tin oxide layer was 40 nm. The mass percentage of tin oxide in the indium tin oxide layer was 5%. Finally, ITO / Cu / ITO sandwich back electrode was prepared by magnetron sputtering. The thickness of the back electrode was 100 nm, and the perovskite solar cell was obtained.

[0084] Example 6

[0085] The difference between the method for preparing perovskite solar cells in Example 6 and Example 1 is that an indium tin oxide layer is deposited on the electron transport layer by electron beam deposition, the thickness of the obtained indium tin oxide layer is 80 nm, and the mass ratio of tin oxide in the indium tin oxide layer is 10%.

[0086] Example 7

[0087] The difference between the method for preparing perovskite solar cells in Example 7 and Example 2 is that an indium tin oxide layer is deposited on the electron transport layer by electron beam deposition, the thickness of the obtained indium tin oxide layer is 80 nm, and the mass ratio of tin oxide in the indium tin oxide layer is 3%.

[0088] Example 8

[0089] The difference between the method for preparing perovskite solar cells in Example 8 and Example 3 is that an indium tin oxide layer is deposited on the electron transport layer by electron beam deposition, the thickness of the obtained indium tin oxide layer is 80 nm, and the mass percentage of tin oxide in the indium tin oxide layer is 5%.

[0090] Example 9

[0091] The difference between the method for preparing perovskite solar cells in Example 9 and Example 4 is that an indium tin oxide layer is deposited on the electron transport layer by electron beam deposition, the thickness of the obtained indium tin oxide layer is 80 nm, and the mass percentage of tin oxide in the indium tin oxide layer is 8%.

[0092] Example 10

[0093] The difference between the methods for preparing perovskite solar cells in Example 10 and Example 5 is that an indium tin oxide layer is deposited on the electron transport layer by electron beam deposition, the thickness of the obtained indium tin oxide layer is 80 nm, and the mass percentage of tin oxide in the indium tin oxide layer is 5%.

[0094] The electrical performance test results of the perovskite solar cells of Comparative Examples 1-5 and Examples 1-10 are shown in the figure. Figure 4-11 See Table 1.

[0095] Table 1

[0096]

[0097]

[0098] from Figure 4-11As shown in Table 1, comparing the IV test data of the perovskite solar cells in Comparative Examples 1-5 and Examples 1-10 reveals that adding the indium tin oxide (ITO) layer significantly reduces the Rs of the module, greatly increases the cell fill factor, and also improves the Voc and Isc of the cell, indicating a significant improvement in cell efficiency. This demonstrates that adding the ITO layer in this application can effectively improve the photoelectric conversion efficiency of the cell. Furthermore, increasing or decreasing the tin oxide content beyond the optimal mass percentage (5%) in the ITO layer leads to an increase in series resistance, resulting in a decrease in cell fill factor and efficiency. A comparison of the cell results from Examples 3 and 5 shows that selecting an appropriate ITO layer thickness and the optimal fabrication process can effectively improve cell efficiency.

[0099] The light transmittance test results for the indium tin oxide layers of Examples 6-10 and Comparative Examples 4-5 are shown below. Figure 12 .

[0100] from Figure 12 It can be seen that in Examples 6-9 and Comparative Examples 4-5, when the mass percentage of tin oxide in the indium tin oxide layer is between 3% and 10%, the light transmittance of the corresponding indium tin oxide single film is improved, and the light transmittance of the indium tin oxide single film corresponding to the mass percentage of tin oxide (5%) is optimal. In Example 10, the light transmittance of the single film can be further improved by introducing process gas and using ion source-assisted deposition.

[0101] The resistivity test results of the indium tin oxide layers of Examples 6-10 and Comparative Examples 4-5 are shown in Table 2.

[0102] Table 2

[0103] Film thickness(nm) Shear resistance Ω / □ Resistivity (Ω*cm) Example 6 80 1327 <![CDATA[1.06×10 -2 ]]> Example 7 80 526 <![CDATA[4.21×10 -3 ]]> Example 8 80 450 <![CDATA[3.60×10 -3 ]]> Example 9 80 510 <![CDATA[4.08×10 -3 ]]> Example 10 80 122.1 <![CDATA[9.77×10 -4 ]]> Comparative Example 4 80 1432 <![CDATA[1.15×10 -2 ]]> Comparative Example 5 80 1420 <![CDATA[1.14×10 -2 ]]>

[0104] As can be seen from Table 2, in Examples 6-9 and Comparative Examples 4-5, the resistivity of the corresponding Indium Tin Oxide (ITO) monolayer is lowest when the mass percentage of tin oxide in the ITO layer is 5% (Example 8). Further increasing or decreasing the mass percentage of tin oxide in the ITO layer will increase the resistivity of the corresponding ITO monolayer. In Example 10, based on the optimal mass percentage of tin oxide (5%), the resistivity of the ITO monolayer can be further reduced and its conductivity improved by introducing process gas and using ion source-assisted deposition.

[0105] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0106] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing perovskite solar cells, characterized in that, include: (1) A hole transport layer, a perovskite absorption layer and an electron transport layer are sequentially formed on a transparent conductive film glass substrate; (2) An indium tin oxide layer is formed on the electron transport layer using electron beam deposition; (3) A back electrode is formed on the indium tin oxide layer. The electron beam deposition method includes ionizing the process gas using an auxiliary electron beam ion source device, so that the ionized ions are doped into the indium tin oxide layer. The perovskite solar cell comprises, in sequence, a transparent conductive film, a hole transport layer, a perovskite absorber layer, an electron transport layer, an indium tin oxide layer, and a back electrode. The indium tin oxide layer contains 3% to 10% tin oxide by mass.

2. The method according to claim 1, characterized in that, The hole transport layer has a thickness of 5-50 nm, the perovskite absorber layer has a thickness of 100-1000 nm, the electron transport layer has a thickness of 5-50 nm, and the back electrode has a thickness of 50-300 nm.

3. The method according to claim 1, characterized in that, The thickness of the indium tin oxide layer is 10 nm to 200 nm.

4. The method according to claim 1, characterized in that, In step (2), the electron beam deposition method includes: placing the sample obtained in step (1), which includes a transparent conductive film, a hole transport layer, a perovskite absorption layer and an electron transport layer, on a rotating platform, using indium tin oxide as a precursor material, and sublimating the indium tin oxide under the action of an electron beam emitted by an electron gun, so as to form an indium tin oxide layer on the electron transport layer of the sample.

5. The method according to claim 4, characterized in that, The rotating platform has a rotational speed of 0~20 r / min, a deposition rate of 0.1~1.0 Å / s, and a deposition temperature of 50~300℃.

6. The method according to claim 1, characterized in that, The flow rate of the process gas is 3~50 sccm.

7. The method according to claim 1, characterized in that, The process gas includes at least one of argon, nitrogen, oxygen, and an argon-oxygen mixture.

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