Method for preparing high-stability inorganic perovskite solar cell

Abstract

A method for preparing a high-stability inorganic perovskite solar cell. The method comprises the steps of: using a radio-frequency (RF) ion source to remove impurities from the surface of a substrate; performing ion source-assisted RF magnetron sputtering to prepare an ITO electrode on the substrate, performing ion source-assisted RF magnetron sputtering to prepare a hole transport layer and a hole modification layer, performing electron cyclotron resonance source-assisted RF magnetron sputtering to prepare a perovskite absorption layer, performing ion source-assisted RF magnetron sputtering to prepare an electron transport layer, performing RF magnetron sputtering to prepare a barrier buffer layer, performing RF magnetron sputtering to prepare a top electrode, and then performing encapsulation. Compared with the prior art, the present application achieves higher efficiency, better stability and greater flexibility.

Description

Preparation method of high-stability inorganic perovskite solar cell

[0001] The present application claims priority to the Chinese patent application No. 202410475323.X filed on April 19, 2024, and entitled "Preparation method of all-inorganic perovskite solar cell", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the field of solar cells, in particular to a preparation method of high-stability inorganic perovskite solar cell. BACKGROUND

[0003] With the increasing demand for renewable energy worldwide, solar cells as an important clean energy device have attracted widespread attention in research and application. Among them, perovskite solar cells have become one of the research hotspots due to their high efficiency, low cost and easy preparation. Perovskite is a material with ABX3 structure, where A and B are cations and X is an anion. In solar cells, perovskite is usually used as a light-absorbing layer, which can effectively absorb sunlight and generate electron - hole pairs. In addition, inorganic materials are widely used in the preparation of solar cells due to their stability and reliability.

[0004] The existing preparation technology of perovskite solar cells mainly includes solution method and vacuum method. Solution method mainly prepares perovskite thin film on the substrate by spin coating, blade coating and other methods, and then crystallizes the thin film by heat treatment and other methods. Vacuum method mainly prepares perovskite thin film on the substrate by sputtering, evaporation and other methods. Both methods have their own advantages and disadvantages, for example, the advantages of solution method are simple equipment and low cost, but the quality of the prepared thin film is not as good as that of vacuum method; while the advantages of vacuum method are that the thickness and composition of the thin film can be accurately controlled, but the equipment is complex and the cost is high.

[0005] Therefore, although the existing preparation technology of perovskite solar cells has made certain progress, there are still some problems and challenges. For example: 1) The existing preparation method often needs to use organic solvents, which not only increases the production cost, but also may cause environmental pollution. 2) The existing preparation method often needs to be carried out at high temperature, which may cause the decomposition of perovskite thin film and affect the performance of the cell. 3) In addition, the existing preparation method often cannot realize large-area and uniform thin film preparation, which also limits the large-scale application of perovskite solar cells. SUMMARY

[0006] The present application is to solve at least one of the above problems to some extent, and provides a preparation method of high-stability inorganic perovskite solar cell.

[0007] The application provides the following technical solutions:

[0008] In a first aspect, the application provides a high-stability inorganic perovskite solar cell preparation method, including the following steps:

[0009] S1, place the glass substrate to be treated into a first plasma chamber CB1, turn on a radio frequency ion source RL1, set the power to 100-300 W, and the time to 10-30 minutes, to remove impurities on the surface of the substrate;

[0010] S2, vacuumize before coating, prepare an ITO film on the cleaned glass substrate, use a cathode target ITO, the power of a radio frequency power source RP1 is 50-200 W, the chamber is heated to 100-200 DEG C for preparation, and sputtering is performed under a working pressure of 0.1-0.8 Pa; meanwhile, use a target indium oxide or silver, assist in doping the indium oxide or silver by using an ion source L1, the power of the ion source L1 is 10-200 W, so as to improve the light transmittance of the ITO electrode, the two targets are placed oppositely, and an ITO electrode with a thickness of 100-400 nm is prepared;

[0011] S3, start a radio frequency power source RP2 and a radio frequency power source RP3, the corresponding target cathodes of the two radio frequency power sources are selected from any one of Ni, NiO, Mo, MoO3, V, Co, Fe and Cu, different targets are used for the two radio frequency power sources, the two targets are placed oppositely, co-sputtering is performed, room temperature preparation is performed, the power of the two radio frequency power sources RP2 and RP3 is 20-100 W, sputtering is performed under a working pressure of 0.1-1.5 Pa, a hole transport layer with a thickness of 10-100 nm is prepared, and then in-situ annealing is performed on the hole transport layer;

[0012] S4, use atomic layer deposition or magnetron sputtering to prepare a TiO2 film layer, a ZnO film layer or a NiO X film layer on the surface of the hole transport layer, a hole modification layer with a thickness of 1-10 nm is obtained, and then in-situ annealing is performed;

[0013] S5, start a radio frequency power source RP4 and a radio frequency power source RP5, the corresponding target cathodes of the two radio frequency power sources are selected from one or more of Cs, Sn, Rb, K and Pb, the two planar target cathodes are placed oppositely, co-sputtering is performed, room temperature preparation is performed, the power of the two radio frequency power sources RP4 and RP5 is 20-200 W, sputtering is performed under a working pressure of 0.1-1.5 Pa, meanwhile, an electron cyclotron resonance (ECR) source is started, any one or two of I, Br and Cl is introduced, ECR-assisted sputtering is performed under a power of 20-200 W, a perovskite absorption layer with a thickness of 300-700 nm is prepared, and then annealing is performed on the perovskite absorption layer;

[0014] S6, start the radio frequency power supply RP6 and the radio frequency power supply RP7, both corresponding to select the target material cathode as any one of Ti, TiO2, Zn, ZnO, Sn, Al and W, two radio frequency power supplies RP6, RP7 use different target materials, carry out co-sputtering, room temperature preparation, the power of two radio frequency power supplies RP6, RP7 is 20W-200W, sputtering adopts different power, sputtering under 0.1Pa-0.5Pa working pressure, prepare 10nm-100nm thin film as electron transport layer, when starting the radio frequency power supply RP7, connect into an ion source L2, both share the cathode;

[0015] S7, start the radio frequency power supply RP8 and the ion source L3, the radio frequency power supply RP8 corresponds to select a planar cathode, any one of Sn, SnIn, SnZn and SnO2 can be installed on the target material, the ion source L3 is connected to O2, N2O or CF4 to assist sputtering; Start the radio frequency power supply RP8 and the ion source L3 at room temperature, the power of the radio frequency power supply RP8 is 10W-100W, the power of the ion source L3 is 10W-100W, sputtering under 0.1Pa-1.5Pa working pressure using the ion source L3 assisted sputtering, prepare 2nm-70nm blocking buffer layer;

[0016] S8, start the radio frequency power supply RP9, the radio frequency power supply RP9 corresponds to select a planar cathode, any one of Ag, Au, Cu and Al can be installed on the target material or alloy target material or TCO target material for sputtering, the sputtering power is 10W-300W, sputtering at room temperature, 0.1P-1.5Pa working pressure, and then prepare 2nm-500nm top electrode;

[0017] S9, package the battery by using a laminator to obtain a high-stability inorganic perovskite solar cell, the package uses EVA, and hollow glass beads are added in the EVA.

[0018] In a possible implementation, the annealing temperature in S3 is 200℃-300℃.

[0019] In a possible implementation, the annealing temperature in S4 is 100℃-200℃.

[0020] In a possible implementation, in S5, the annealing is first heated to 50℃-70℃, and then heated to 100℃-120℃ after being stabilized for 5 minutes, so as to complete the annealing of the perovskite absorption layer.

[0021] In a possible implementation, the diameter of the hollow glass bead in S9 is 1μm-10μm.

[0022] In a possible implementation, the vacuum degree in S2 to S8 steps can be the same or different.

[0023] In a possible implementation, the target cathode of the radio frequency power source RP1 and the ion source L1 in S2 forms an acute angle with the vertical line of the glass substrate, and the acute angle ranges from 45° to 85°.

[0024] In a possible implementation, the target cathode of the radio frequency power source RP2 and the radio frequency power source RP3 in S3 forms an acute angle with the vertical line of the glass substrate, and the acute angle ranges from 45° to 85°.

[0025] In a possible implementation, the target cathode of the radio frequency power source RP4 and the radio frequency power source RP5 in S5 forms an acute angle with the vertical line of the glass substrate, and the acute angle ranges from 45° to 85°.

[0026] In a possible implementation, the target cathode of the radio frequency power source RP6 and the radio frequency power source RP7 in S6 forms an acute angle with the vertical line of the glass substrate, and the acute angle ranges from 45° to 85°.

[0027] In a second aspect, the embodiments of the present application provide a high-stability inorganic perovskite solar cell preparation method, including the following steps:

[0028] S1, the glass substrate to be processed is placed in the chamber CB1, the radio frequency ion source RL1 is started, the power is set to 100W-300W, and the working time is 10 minutes - 30 minutes, the impurities on the surface of the glass substrate are removed;

[0029] S2, the chamber CB2 is vacuumized, and an ITO film is prepared on the glass substrate: the power of the radio frequency power source RP1 is set to 50W-200W, and the target cathode is ITO; the power of the ion source L1 is set to 10W-200W, and the target cathode is indium oxide or silver; the chamber CB2 is heated to 100℃-200℃, ITO sputtering is performed under a working pressure of 0.1Pa-0.8Pa, and indium oxide or silver is doped, so that an ITO electrode with a thickness of 100nm-400nm is prepared;

[0030] S3, a hole transport layer is prepared on the ITO film in the chamber CB3: the power of the radio frequency power source RP2 and the radio frequency power source RP3 is set to 20W-100W, the target cathodes of the two are selected from any one of Ni, NiO, Mo, MoO3, V, Co, Fe and Cu, and the two use different target cathodes, and the radio frequency power source RP2 and the radio frequency power source RP3 are used for co-sputtering under room temperature and a working pressure of 0.1Pa-1.5Pa, so that a hole transport layer with a thickness of 10nm-100nm is prepared, and then the hole transport layer is annealed in situ;

[0031] S4, in the chamber CB4, a hole modification layer is prepared on the hole transport layer: a 1nm-10nm hole modification layer is prepared on the surface of the hole transport layer by atomic layer deposition or magnetron sputtering, and then in-situ annealing is performed; wherein the hole modification layer is a TiO2 film layer, a ZnO film layer or a NiO X film layer;

[0032] S5, in the chamber CB5, a perovskite absorption layer is prepared on the hole modification layer: the power of the radio frequency power supply RP4 and the radio frequency power supply RP5 is set to 20W-200W, the target cathode of the two is selected from one or more of Cs, Sn, Rb, K and Pb, the two planar target cathodes are oppositely placed, and co-sputtering is performed at room temperature and a working pressure of 0.1Pa-1.5Pa; and an electron cyclotron resonance ECR source is started, and any one or two of I, Br and Cl gas is introduced, the electron cyclotron resonance ECR source is assisted sputtering at a power of 20W-200W, and a perovskite absorption layer with a thickness of 300nm-700nm is prepared, and then the perovskite absorption layer is annealed;

[0033] S6, in the chamber CB6, an electron transport layer is prepared on the perovskite absorption layer, the power of the radio frequency power supply RP6 and the radio frequency power supply RP7 is set to 20W-200W, the power of the two is different, the target cathode of the two is any one of Ti, TiO2, Zn, ZnO, Sn, Al and W, and the target cathode materials of the two are different; at room temperature and a working pressure of 0.1Pa-0.5Pa, the radio frequency power supply RP6 and the radio frequency power supply RP7 co-sputter to prepare a 10nm-100nm thin film as an electron transport layer; wherein an ion source L2 is connected when the radio frequency power supply RP7 is started, and the ion source L2 and the radio frequency power supply RP7 share a cathode;

[0034] S7, in the chamber CB7, a blocking buffer layer is prepared on the electron transport layer: the power of the radio frequency power supply RP8 and the ion source L3 is set to 10W-100W, the target cathode of the radio frequency power supply RP8 is any one of Sn, SnIn, SnZn and SnO2, at room temperature and a working pressure of 0.1Pa-1.5Pa, the radio frequency power supply RP8 sputters, and the ion source L3 is connected to O2, N2O or CF4 for assisted sputtering to prepare a 2nm-70nm blocking buffer layer;

[0035] S8, in the chamber CB8, a top electrode is prepared on the blocking buffer layer: the power of the radio frequency power supply RP9 is set to 10W-300W, the target cathode is any one of Ag, Au, Cu and Al single metal or alloy target material, or the target cathode is a TCO target material, and the radio frequency power supply RP9 sputters at room temperature and a working pressure of 0.1Pa-1.5Pa to prepare a 2nm-500nm top electrode.

[0036] S9, using a laminator to package the current substrate to obtain a high stability inorganic perovskite solar cell, wherein the packaging uses ethylene-vinyl acetate copolymer EVA material, and the EVA has hollow glass beads, and the current substrate is part of the high stability inorganic perovskite solar cell prepared in the current step.

[0037] In one possible implementation, the chamber CB2 and the chamber CB5 are the same chamber, the chamber CB3 and the chamber CB6 are one chamber; the chamber CB4 and the chamber CB8 are one chamber.

[0038] Advantages of the application:

[0039] The application avoids the use of organic solvents, reduces production costs, and also reduces environmental pollution by using physical vapor deposition to prepare perovskite solar cells; by using an electron cyclotron resonance source for co-sputtering in the sputtering process, a high-performance ion source is formed, thereby stabilizing the absorption layer structure and improving the stability of the perovskite solar cell. BRIEF DESCRIPTION OF DRAWINGS

[0040] The drawings described herein are used to provide further understanding of the application, and form a part of the application. The schematic embodiments of the application and their descriptions are used to explain the application, and do not constitute an improper limitation on the application.

[0041] FIG. 1 is a flow chart of a high stability inorganic perovskite solar cell preparation method according to the application;

[0042] FIG. 2 is an I-V curve diagram of a perovskite solar cell according to Embodiment 1 of the application;

[0043] FIG. 3 is an I-V curve diagram of a perovskite solar cell according to Embodiment 2 of the application. DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the application will be described clearly and completely below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the scope of protection of the application.

[0045] In order to reduce the use of organic solvents in the preparation of perovskite solar cells, reduce environmental pollution and reduce production costs, the application provides a high stability inorganic perovskite solar cell preparation method, including the following steps:

[0046] S1, cleaning the glass substrate in the chamber CB1.

[0047] The glass substrate to be processed is placed in the chamber CB1, the radio frequency ion source RL1 is turned on, the power is set to 100W-300W, and the working time is 10 minutes - 30 minutes, the impurities on the surface of the glass substrate are removed.

[0048] S2, an ITO film is prepared on the glass substrate in the chamber CB2.

[0049] The chamber CB2 is vacuumed, the power of the radio frequency power source RP1 is set to 50W-200W, the target cathode is ITO, the power of the ion source L1 is set to 10W-200W, the target cathode is indium oxide or silver, the chamber CB2 is heated to 100℃-200℃, the radio frequency power source RP1 performs ITO sputtering under a working pressure of 0.1Pa-0.8Pa, the ion source L1 performs indium oxide or silver doping, and an ITO electrode with a thickness of 100nm-400nm is prepared. The planar target cathodes of the radio frequency power source RP1 and the ion source L1 are oppositely placed, an acute angle is formed between the target cathodes and the vertical line of the glass substrate, and in one example, the acute angle is 45°-85°.

[0050] S3, a hole transport layer is prepared on the ITO film in the chamber CB3.

[0051] The power of the radio frequency power source RP2 and the radio frequency power source RP3 is set to 20W-100W, the target cathodes of the two are selected from any one of Ni, NiO, Mo, MoO3, V, Co, Fe and Cu, different target cathodes are used, co-sputtering is performed by the radio frequency power source RP2 and the radio frequency power source RP3 under room temperature and a working pressure of 0.1Pa-1.5Pa, a hole transport layer with a thickness of 10nm-100nm is prepared, and then in-situ annealing is performed on the hole transport layer. The planar target cathodes of the radio frequency power source RP2 and the radio frequency power source RP3 are oppositely placed, an acute angle is formed between the target cathodes and the vertical line of the glass substrate, and in one example, the acute angle is 45°-85°.

[0052] S4, a hole modification layer is prepared on the hole transport layer in the chamber CB4.

[0053] The hole modification layer with a thickness of 1nm-10nm is prepared on the surface of the hole transport layer by atomic layer deposition or magnetron sputtering, and then in-situ annealing is performed. In one example, the annealing temperature can be 100℃-200℃. In another example, the annealing temperature can also be 200℃-300℃. The material used by the atomic layer deposition or the magnetron sputtering can be TiO2, ZnO or NiO X , and the formed hole modification layer is a TiO2 film layer, a ZnO film layer or a NiOX membrane layer.

[0054] S5. In chamber CB5, a perovskite absorption layer is prepared on the hole modification layer.

[0055] The power of the RF power supply RP4 and the RF power supply RP5 is set to 20W to 200W, and the target cathodes of the two are selected from one or more of Cs, Sn, Rb, K and Pb. The two planar target cathodes are placed opposite each other and co-sputtered at room temperature and a working pressure of 0.1Pa to 1.5Pa; and an electron cyclotron resonance (ECR) source is started, and any one or two gases of I, Br, and Cl are introduced. The ECR source assists sputtering at a power of 20W to 200W to prepare a perovskite absorption layer with a thickness of 300nm to 700nm, and then the perovskite absorption layer is annealed. In the annealing process, the perovskite absorption layer can be annealed by first heating to 50℃ to 70℃, stabilizing for 5 minutes, and then heating to 100℃ to 120℃ and stabilizing for 5 minutes, thereby completing the annealing of the perovskite absorption layer. The planar target cathodes of the RF power supply RP4 and the RF power supply RP5 are placed opposite to each other, and an acute angle is formed between the target cathodes and the vertical line of the glass substrate. In one example, the acute angle ranges from 45° to 85°.

[0056] S6. In chamber CB6, an electron transport layer is prepared on the perovskite absorption layer.

[0057] The power of RF power supply RP6 and RF power supply RP7 is set to 20W to 200W, and the power of the two power supplies is different. The target cathodes of the two power supplies are any one of Ti, TiO2, Zn, ZnO, Sn, Al, and W, and the target cathode materials of the two power supplies are different. At room temperature and an operating pressure of 0.1Pa to 0.5Pa, RF power supply RP6 and RF power supply RP7 are co-sputtered to prepare a 10nm to 100nm thin film as an electron transport layer. When RF power supply RP7 is started, an ion source L2 is connected. The planar target cathodes of RF power supply RP6 and RF power supply RP7 are placed relative to each other, forming an acute angle between the target cathodes and the vertical line of the glass substrate. In one example, the acute angle ranges from 45° to 85°.

[0058] S7. In chamber CB7, a blocking buffer layer is prepared on the electron transport layer.

[0059] The power of the radio frequency power supply RP8 and the ion source L3 is set to 10W-100W, the target cathode of the radio frequency power supply RP8 is any one of Sn, SnIn, SnZn and SnO2, the radio frequency power supply RP8 performs sputtering at room temperature and under a working pressure of 0.1Pa-1.5Pa, the ion source L3 is connected to O2, N2O or CF4 to perform auxiliary sputtering, and a 2nm-70nm blocking buffer layer is prepared.

[0060] S8, a top electrode is prepared on the blocking buffer layer in the chamber CB8.

[0061] The power of the radio frequency power supply RP9 is set to 10W-300W, the target cathode is any one of single metal or alloy targets of Ag, Au, Cu and Al, or the target cathode is a TCO target, the radio frequency power supply RP9 performs sputtering at room temperature and under a working pressure of 0.1Pa-1.5Pa, and a 2nm-500nm top electrode is prepared.

[0062] S9, the current substrate is packaged by using a laminator to obtain a high-stability inorganic perovskite solar cell, wherein the current substrate is a part of the high-stability inorganic perovskite solar cell prepared in the current step.

[0063] In one example, the packaging material can use ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer can be doped with hollow glass beads, and the diameter of the hollow glass beads can be 1-10μm. The hollow glass beads have the characteristics of high porosity, light weight, large volume, large specific surface area, low thermal conductivity, excellent mechanical properties and flexibility, and can improve the heat preservation, heat insulation, water isolation and gas isolation capacity of the device after packaging, and the nano-microporous hollow glass beads can also reduce the damage of the lamination temperature to the absorption layer, and improve the battery efficiency and stability. Since the addition of the nano-microporous hollow glass beads can improve the heat preservation, heat insulation, water isolation and gas isolation capacity of the device after packaging, reduce the damage of the lamination temperature to the absorption layer, and improve the battery efficiency and stability.

[0064] In the embodiment of the application, the radio frequency ion source RL1 is used to clean the surface of the glass, and the radio frequency ion source RL1 can generate gas ions to remove surface impurities. The core function is to ionize the gas through the radio frequency electromagnetic field to form a directional high-energy ion flow, so that the glass surface can be cleaned very cleanly, and the cleaning effect is good, and no organic solvent is used. The radio frequency power supplies RP1-RP9 are conventional sputtering power supplies, which focus on high-frequency plasma excitation, have high output power, and are used for growing thin films. The ion sources L1-L3 are used for auxiliary doping, and a small amount of ions is injected or doped into the thin film, and ionization is achieved by directly breaking the gas through high-voltage arc or by bombarding gas molecules through electron beams.

[0065] The application avoids the use of organic solvents, reduces production costs, and also reduces environmental pollution; by precisely controlling sputtering parameters such as power, angle, gas flow, etc., large-area, uniform thin film preparation can be achieved, and the performance of the perovskite solar cell is improved; by using an electron cyclotron resonance source for co-sputtering during sputtering, a high-performance ion source is formed, thereby stabilizing the absorption layer structure and improving the stability of the perovskite solar cell. By adjusting the sputtering parameters, different types of thin films can be easily prepared, improving the flexibility of the preparation process; by optimizing the design and layout of the target material and changing the target sputtering angle, the doping concentration, depth, and sputtering parameters can be adjusted to accurately control the thickness and performance of the thin film, effectively improving the overall uniformity and performance of the thin film solar cell, thereby improving the performance and stability of the solar cell.

[0066] Since the preparation methods have the same parts, in some possible embodiments, the chamber CB2 and the chamber CB5 are the same chamber, the chamber CB3 and the chamber CB6 are one chamber; the chamber CB4 and the chamber CB8 are one chamber, thereby saving space, saving equipment, and reducing production costs.

[0067] The chamber CB2 and the chamber CB5 can be the same chamber, and in steps S2 and S5, two planar target cathodes need to be placed opposite to each other for magnetron sputtering, i.e., two planar target cathodes of the radio frequency power source RP1 and the ion source L1 are placed opposite to each other, and two planar target cathodes of the radio frequency power source RP4 and the radio frequency power source RP5 are placed opposite to each other. Therefore, in S2 and S5, one chamber can be shared by steps S2 and S5 by replacing the target material. The chamber CB3 and the chamber CB6 can be the same chamber, and steps S3 and S6 both need two planar target cathodes to be placed opposite to each other for magnetron sputtering, so in S3 and S6, one chamber can be shared by steps S3 and S6 by replacing the target material. When the magnetron sputtering preparation method is used in step S4, the chamber CB4 and the chamber CB8 can be the same chamber, and S4 and S8 both use only one planar target for magnetron sputtering, and when shared, only the target material needs to be replaced after the end of step S4 and adjusted to the parameters required by S8.

[0068] Of course, in other possible embodiments, the chambers CB1-CB8 can all be different chambers.

[0069] The RF power source in the present application is connected with the ion source, which means that the RF power source shares the cathode with the ion source; the RF power source is connected with the ECR source, which means that the RF power source shares the cathode with the ECR source. In some possible scenarios, the RF power source can share the cathode with the ion source or the ECR, and can share the gas flow meter channel when controlling the gas flow. Among the multiple RF power sources, at least 4 movable RF power sources, 2 movable ion sources, and 1 movable ECR source are needed, that is, ion source assisted magnetron sputtering can be performed. Specifically, the RF power sources RP1-RP4 can share any one of the RF power sources RP5-RP9, for example, the RF power sources RP1-RP4 can be used to perform the functions of the RF power sources RP5-RP8 (wherein the RF power source RP4 and the RF power source RP5 are different RF power sources because both of them are used in step S5, and one of the RF power sources RP1-RP3 can be used to perform the function of the RF power source RP5, for example, the RF power source RP1 is used to perform the function of the RF power source RP5, that is, the RF power source RP1 is used to perform the function of the RF power source RP5 with one RF power source), and after step S5 is completed, the RF power source RP4 or RP5 is used to perform the function of the RF power source RP9. Any one of the ion sources L1 and L2 can be used to perform the function of the ion source L3. In the embodiment of the present application, the thin film can be prepared in a low electron beam energy and high ionization rate environment, which reduces sputtering damage, ion damage, etc., and does not affect the denseness of the underlying thin film.

[0070] Hereinafter, the preparation method of the high-stability inorganic perovskite solar cell is exemplified:

[0071] Embodiment 1

[0072] As shown in FIGS. 1 and 2, the embodiment of the present application provides a preparation method of a high-stability inorganic perovskite solar cell, which comprises the following steps:

[0073] Step one: place the glass substrate (also referred to as glass substrate) to be treated into the first plasma chamber CB1, turn on the RF (Radio Frequency) ion source RL1, introduce argon gas with a power of 300 W, and set the time to 15 minutes to clean the impurities on the surface of the glass substrate.

[0074] Step two: enter the chamber CB2, and vacuumize to a background vacuum degree of 3x10- 4Pa; for preparing ITO film on the cleaned glass substrate, ITO target material is used, the power of RF power supply RP1 is 100 W, the chamber CB2 is heated to 200 ℃, 30 sccm (standard cubic centimeter per minute) high-purity argon (Ar) gas is introduced as sputtering gas, and sputtering is performed under a working pressure of 0.5 Pa; at the same time, 100 W ion source is used to dope In2O3, and an ITO electrode doped with In2O3 with a thickness of 210 nm is obtained.

[0075] First, the chamber CB2 is pumped to a background vacuum degree of 3x10- 4 Pa, then 30 sccm high-purity argon gas is introduced as sputtering gas, so that the working pressure in the chamber is 0.5 Pa, and the chamber is heated to 200 ℃; the power of RF power supply RP1 is set to 100 W, ITO film is prepared on the glass substrate under a working pressure of 0.5 Pa, and In2O3 is sputtered using RF ion power supply R3 with a power of 100 W, so that an ITO electrode doped with In2O3 with a thickness of 210 nm is finally formed on the glass substrate. In the ITO electrode, the mass ratio of In2O3 to SnO2 can be 90:10.

[0076] Step three: enter the chamber CB3, pump to a background vacuum degree of 3x10- 4 Pa before coating, start the self-rotation device, set the power of RF power supply RP2 to 100 W, the target material is Ni, and set the power of RF power supply RP3 to 80 W, the target material is V; introduce 30 sccm high-purity argon gas as sputtering gas, connect the ion source to high-purity oxygen (O2) as reaction gas, and fully ionize it, and perform co-sputtering under a working pressure of 0.5 Pa (the ion source can also be connected to the cathode of RF power supply RP3 to fully ionize metal V; then, all power supplies are turned off, the chamber is heated to 200 ℃, and after stabilization, it is kept for 10 minutes, so that a 20 nm thick NiO x -V film is prepared as a hole transport layer.

[0077] Step four: enter the chamber CB4, pump to a background vacuum degree of 1.5x10- 4 Pa before coating, use 99.7% diethyl zinc and water as the source, diethyl zinc as the Zn source, 99.999% N2 as the carrier gas, deionized water as the O source, the pressure in the chamber is kept at 10 Pa to 25 Pa, and the deposition temperature is 50 ℃ to 80 ℃; one ALD (Atomic Layer Deposition) cycle of ZnO is 0.01 s to 0.04 s of DEZn (diethyl zinc) pulse, 15 s to 35 s of purging, 0.01 s to 0.03 s of H2O pulse, and 15 s to 35 s of purging; and the cycle is repeated to prepare a 2 nm thick ZnO film as a hole modification layer. Then, the sample is heated to 150 ℃ in situ for annealing.

[0078] Step five: enter the chamber CB5, vacuum to the background vacuum degree 3 x 10- 4 Pa, open the rotation device, open the radio frequency power supply RP4, set the power to 300W, install the CsPb (mass ratio 1:1) alloy target, open the radio frequency power supply RP5, set the power to 30W, install the Sn target, adjust the radio frequency power supply RP4, RP5 target cathode and the vertical line angle of the substrate to 80°, input 30sccm high purity argon as sputtering gas, perform co-sputtering under 0.5Pa working pressure; connect the electron cyclotron resonance source to high purity iodine gas (I2): bromine gas (Br2) = 2:1 (volume ratio) as the reaction gas, make it fully dissociated to form a high performance ion source for co-sputtering, and perform absorption layer preparation on the NiOx-V thin film, and after the radio frequency power supply RP4, RP5 sputtering power supply is turned off, the electron cyclotron resonance source is maintained open for 3min to stabilize the absorption layer structure, and a 450nm thick CsPbI2Br-Sn film is prepared as a perovskite absorption layer; then, the chamber is heated to 80℃ at the original position, and after stabilization, it is maintained for 5min, and then heated to 140℃ and maintained for 10min.

[0079] Step six: enter the chamber CB6, vacuum to the background vacuum degree 3 x 10- 4 Pa, open the radio frequency power supply RP6, set the power to 200W, install the W target, open the radio frequency power supply RP7 and connect the ion source L2 (common cathode), set the power to 30W, install the Ti target, make it fully dissociated, adjust the radio frequency power supply RP6, RP7 target cathode and the vertical line angle of the substrate to 85°, input 30sccm high purity argon (Ar) as sputtering gas, input O2 as reaction gas, perform co-sputtering under 0.5Pa working pressure to prepare a 60nm thick WO X -Ti thin film as an electron transport layer.

[0080] Step seven: enter the chamber CB7, vacuum to the background vacuum degree 3 x 10- 4 Pa, open the radio frequency power supply RP8, set the power to 100W, install the SnO2:In2O3 = 99:1 (mass ratio) target at the same time, input 30sccm high purity argon Ar as sputtering gas; at the same time, the ion source L3 is connected to nitrous oxide (N2O) gas, input N2O flow of 3sccm, perform ion source assisted sputtering; perform sputtering under 0.7Pa working pressure to prepare a 30nm thick SnO2:In2O3 thin film, which is not conductive, but the light transmission performance is greatly improved compared with a single SnO2 thin film.

[0081] Step eight: enter the chamber CB8, vacuum to the background vacuum degree 3 x 10- 4Pa, open the RF power source RP9, set the power to 50 W, at the same time install the Ag: Cu = 96%: 4% (mass ratio) alloy target material, input 30 sccm high-purity argon, carry out sputtering under the working pressure of 0.6 Pa to prepare the AgCu alloy thin film with the thickness of about 20 nm.

[0082] Step nine: use EVA (Ethylene-Vinyl Acetate Copolymer) to mix with hollow glass beads with the diameter of 3 μm as the packaging material, and package the battery in the laminator.

[0083] The obtained perovskite solar cell has V oc (open circuit voltage) = 79.21 V, I sc (maximum current value under standard conditions) = 2.5776 A, FF (Fill Factor) = 64.01%, and the photoelectric conversion efficiency (η) is 12.4%.

[0084] Example 2

[0085] As shown in FIG. 1 and FIG. 3, the application provides a high-stability inorganic perovskite solar cell preparation method, which comprises the following steps:

[0086] Step one: place the glass substrate to be treated into the first plasma chamber CB1, open the video ion source RL1, set the power to 200 W, and the time to 25 minutes to clean the impurities on the surface of the substrate.

[0087] Step two: enter the chamber CB2, vacuumize to the background vacuum degree of 2x10- 4 Pa, prepare the ITO: Ag thin film from the cleaned glass substrate, the RF power source RP1 has the power of 100 W, the chamber CB2 is heated to 300 ℃ for preparation, input 30 sccm high-purity argon (Ar) as the sputtering gas, at the same time, use the 10 W ion source L1 to connect Ag, sputter under the working pressure of 0.35 Pa to obtain the 110 nm ITO-Ag electrode.

[0088] Step three: enter the chamber CB3, vacuumize to the background vacuum degree of 2x10- 4 Pa, open the self-rotation device, the RF power source RP2 and the ion source share the cathode, the target cathode is Mo, set the RF power source RP3 to 150 W to fully separate the metal Mo; the RF power source RP3 has the power of 20 W, the target cathode is Cu; input high-purity argon (Ar) as the sputtering gas and high-purity oxygen (O2) as the reaction gas, carry out co-sputtering under the working pressure of 0.35 Pa; then, close all power sources, heat the chamber to 150 ℃, keep for 15 minutes after stabilization to make the thin film fully nucleate and crystallize, and prepare the 25 nm MoOx Cu thin film as a hole transport layer.

[0089] Step four: enter chamber CB4, vacuum to the background vacuum degree 6x10- 4 Pa, using Ti target, high-purity oxygen gas as the reaction gas, Ar as the sputtering gas, and a working pressure of 0.35 Pa at room temperature to perform magnetron sputtering to prepare a 5-nm hole modification layer. Then, the sample is heated to 120 DEG C in situ for annealing.

[0090] Step five: enter chamber CB5, vacuum to the background vacuum degree 1x10- 4 Pa, turn on the self-rotating device, turn on the RF power source RP4, set the power to 200 W, install the CsPbSn (mass ratio 3:1:1) alloy target material, connect the RF power source RP5 to the electron cyclotron resonance source, adjust the vertical angle between the target cathode and the substrate to 75 DEG, set the RF power source RP5 power to 20 W, install the K target material, introduce high-purity argon gas as the sputtering gas, and high-purity iodine gas I2: chlorine gas Cl2 = 1:2 (volume ratio) as the reaction gas to form a high-performance K ion source, and perform co-sputtering under a working pressure of 0.35 Pa. The doping of K is beneficial to the carrier activity of the perovskite absorption layer, and after the RF power sources RP4 and RP5 are turned off, the electron cyclotron resonance source is maintained for 1 min to stabilize the absorption layer structure, and a 500-nm-thick CsPbSnCl3 -x I x K thin film as a perovskite absorption layer.

[0091] The prepared CsPbSnCl 3-x I x The K thin film is heated in situ by turning on the substrate holder, first heated to 50 DEG C, and then maintained for 2 min, and then heated to 110 DEG C and maintained for 20 min.

[0092] Step six: enter chamber CB6, vacuum to the background vacuum degree 2x10- 4 Pa, turn on the RF power source RP6 and set the power to 100 W, install the Al target material, turn on the RF power source RP7 and connect the ion source L2 (common cathode), set the power to 20 W, install the Zn target material, and make it fully isolated, introduce high-purity argon gas as the sputtering gas, and introduce O2 as the reaction gas, and perform co-sputtering under a working pressure of 0.35 Pa to prepare a 40-nm-thick AlO X Zn thin film as an electron transport layer, and the vertical angle between the target cathode and the substrate is adjusted to 80 DEG.

[0093] Step seven: enter chamber CB7, vacuum to the background vacuum degree 2x10- 4Pa, open the radio frequency power supply RP8 and connect the ion source L3, set the power to 80W, at the same time install Sn:Zn=99.5%:0.5%(mass ratio) target material, high-purity argon Ar is introduced as sputtering gas, O2 is introduced as reaction gas, and sputtering is carried out; at the same time, the ion source L3 is connected with CF4 gas, and the CF4 flow is 4sccm, ion source assisted sputtering is carried out; sputtering is carried out under 0.5Pa working pressure, so as to prepare 30nm thick SnO2-ZnO thin film, the thin film is not conductive, but the light transmission performance is greatly improved compared with single SnO2 thin film.

[0094] Step eight: enter the chamber CB8, vacuumize to the background vacuum degree 4x10- 4 Pa, open the radio frequency power supply RP9, set the power to 50W, at the same time install Au:Cu=96%:2%(mass ratio) alloy target material, sputtering is carried out, so as to prepare AuCu alloy thin film with thickness of about 130nm.

[0095] Step nine: EVA is mixed with hollow glass beads with diameter of 5μm as packaging material, and the battery is packaged in the laminating machine.

[0096] The obtained perovskite solar cell, V oc =78.16V, I sc =2.63A, FF=64.29%, and the photoelectric conversion efficiency(η) is 12.52%.

[0097] The above only describes the preferred embodiments of the present application, and does not limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a high-stability inorganic perovskite solar cell, characterized by, The method comprises the following steps: S1, placing a glass substrate to be treated into a first plasma chamber, starting a radio frequency ion source, setting the power to 100-300 W, and setting the time to 10-30 minutes to remove impurities on the surface of the substrate; S2, vacuumizing before coating, preparing an ITO film on the cleaned glass substrate, setting the power of the radio frequency power source RP1 to 50-200 W, heating the chamber to 100-200 DEG C for preparation, and sputtering under a working pressure of 0.1-0.8 Pa; meanwhile, doping indium oxide or silver by using the ion source L1, setting the power to 10-200 W, so as to improve the light transmittance of the ITO electrode, and preparing an ITO electrode with a thickness of 100-400 nm; S3, starting the radio frequency power sources RP2 and RP3, selecting any one of Ni, NiO, Mo, MoO3, V, Co, Fe and Cu as the target cathode corresponding to the radio frequency power sources RP2 and RP3, using different target materials for the two radio frequency power sources RP2 and RP3 for co-sputtering, preparing at room temperature, setting the power of the two radio frequency power sources to 20-100 W, sputtering under a working pressure of 0.1-1.5 Pa, preparing a hole transport layer with a thickness of 10-100 nm, and then performing in-situ annealing on the hole transport layer; S4, TiO2, ZnO or NiO is prepared on the surface of the hole transport layer by atomic layer deposition or magnetron sputtering X to obtain a 1nm-10nm hole modification layer, and then in-situ annealing is performed; S5, starting the radio frequency power sources RP4 and RP5, selecting one or more of Cs, Sn, Rb, K and Pb as the target material corresponding to the radio frequency power sources RP4 and RP5, placing the two planar target cathodes oppositely, co-sputtering, preparing at room temperature, setting the power of the two radio frequency power sources RP4 and RP5 to 20-200 W, sputtering under a working pressure of 0.1-1.5 Pa, simultaneously, starting the electron cyclotron resonance (ECR) source, inputting any one or two of I, Br and Cl, ECR assisted sputtering under a power of 20-200 W to prepare a perovskite absorption layer with a thickness of 300-700 nm, and then performing annealing on the perovskite absorption layer; S6, starting the radio frequency power sources RP6 and RP7, selecting any one of Ti, TiO2, Zn, ZnO, Sn, Al and W as the target material corresponding to the radio frequency power sources RP6 and RP7, using different target materials for the two radio frequency power sources RP6 and RP7 for co-sputtering, preparing at room temperature, setting the power of the two radio frequency power sources RP6 and RP7 to 20-200 W, sputtering with different powers, sputtering under a working pressure of 0.1-0.5 Pa, preparing a thin film with a thickness of 10-100 nm as an electron transport layer, and connecting the ion source L2 when starting the radio frequency power source RP7, the two sharing the cathode; S7, starting the radio frequency power source RP8 and the ion source L3, selecting any one of Sn, SnIn, SnZn and SnO2 as the target material corresponding to the radio frequency power source RP8, and connecting O2, N2O or CF4 to the ion source L3 for auxiliary sputtering; simultaneously starting the radio frequency power source RP8 and the ion source L3 at room temperature, setting the power of the radio frequency power source RP8 to 10-100 W, auxiliary sputtering under a working pressure of 0.1-1.5 Pa, setting the power of the ion source L3 to 10-100 W, and preparing a blocking buffer layer with a thickness of 2-70 nm. S8, start the radio frequency power supply RP9, the radio frequency power supply RP9 corresponds to select the single metal or alloy target material of any one of Ag, Au, Cu and Al or the TCO target material on the cathode to carry out sputtering, the sputtering power is 10W~300W, and the working pressure is 0.1Pa~1.5Pa, and then the top electrode of 2nm~500nm is prepared; S9, the battery is packaged by using a laminator to obtain a high-stability inorganic perovskite solar cell, and EVA is used for packaging, and hollow glass beads are added in the EVA.

2. The method for preparing a high-stability inorganic perovskite solar cell according to claim 1, characterized in that: The annealing temperature in S3 is 200 DEG C~300 DEG C.

3. The method for preparing a high-stability inorganic perovskite solar cell according to claim 1, characterized in that: The annealing temperature in S4 is 100 DEG C~200 DEG C.

4. The method for preparing a high-stability inorganic perovskite solar cell according to claim 1, characterized in that: In S5, the annealing is first heated to 50 DEG C~70 DEG C, and then heated to 100 DEG C~120 DEG C after 5 minutes of stabilization, so that the annealing of the perovskite absorption layer is completed.

5. The method for preparing a high-stability inorganic perovskite solar cell according to claim 1, characterized in that: The diameter of the hollow glass bead in S9 is 1um~10um.

6. The method for preparing a high-stability inorganic perovskite solar cell according to claim 1, characterized in that: The vacuum degree in S2 to S8 can be the same or different.

7. The method for preparing a high-stability inorganic perovskite solar cell according to claim 1, characterized in that: In S5, the radio frequency power supply RP4 and the radio frequency power supply RP5 form an acute angle between the target cathode and the vertical line of the substrate. 8.The method for preparing a high-stability inorganic perovskite solar cell according to claim 1, characterized in that: In S6, the radio frequency power supply RP6 and the radio frequency power supply RP7 form an acute angle between the target cathode and the vertical line of the substrate.

9. A method for preparing a high-stability inorganic perovskite solar cell, characterized by, The steps include: S1, the glass substrate to be treated is placed in the chamber CB1, the radio frequency ion source RL1 is started, the power is set to 100W-300W, and the working time is 10 minutes-30 minutes, and the impurities on the surface of the glass substrate are removed; S2, the chamber CB2 is vacuumized, and an ITO film is prepared on the glass substrate: the power of the radio frequency power supply RP1 is set to 50W-200W, the target cathode is ITO; the power of the ion source L1 is set to 10W~200W, the target cathode is indium oxide or silver; the chamber CB2 is heated to 100 DEG C-200 DEG C, and ITO sputtering is carried out under a working pressure of 0.1Pa~0.8Pa, and indium oxide or silver is doped, and an ITO electrode of 100nm~400nm is prepared; S3, in the chamber CB3, a hole transport layer is prepared on the ITO film: the power of the radio frequency power supply RP2 and the radio frequency power supply RP3 is set to 20W~100W, the target cathodes of the two are selected from any one of Ni, NiO, Mo, MoO3, V, Co, Fe and Cu, and the two use different target cathodes, and the radio frequency power supply RP2 and the radio frequency power supply RP3 are used for co-sputtering under room temperature and a working pressure of 0.1Pa~1.5Pa, and a hole transport layer of 10nm~100nm is prepared, and then the hole transport layer is annealed in situ; S4, in the chamber CB4, a hole modification layer is prepared on the hole transport layer: a 1nm-10nm hole modification layer is prepared on the surface of the hole transport layer by atomic layer deposition or magnetron sputtering, and then in-situ annealing is performed; wherein the hole modification layer is a TiO2 film layer, a ZnO film layer or a NiO X film layer; S5, in the chamber CB5, on the said hole modification layer, prepare perovskite absorption layer: set the power of RF power supply RP4 and RF power supply RP5 to 20W-200W, the target cathode of the two is selected from one or more of Cs, Sn, Rb, K and Pb, the two planar target cathodes are oppositely placed, and co-sputtering is carried out at room temperature and 0.1Pa-1.5Pa working pressure; and start the electron cyclotron resonance ECR source, input any one or two of I, Br and Cl gas, and the electron cyclotron resonance ECR source is assisted sputtering at 20W-200W power to prepare a perovskite absorption layer with a thickness of 300nm-700nm, and then the perovskite absorption layer is annealed; S6, in the chamber CB6, on the said perovskite absorption layer, prepare an electron transport layer, set the power of RF power supply RP6 and RF power supply RP7 to 20W-200W, the power of the two is different, the target cathode of the two is any one of Ti, TiO2, Zn, ZnO, Sn, Al and W, and the target cathode materials of the two are different; RF power supply RP6 and RF power supply RP7 are co-sputtered at room temperature and 0.1Pa-0.5Pa working pressure to prepare a thin film with a thickness of 10nm-100nm as an electron transport layer; wherein, when the RF power supply RP7 is started, the ion source L2 is connected, and the two share a cathode; S7, in the chamber CB7, on the said electron transport layer, prepare a blocking buffer layer: set the power of RF power supply RP8 and ion source L3 to 10W-100W, the target cathode of RF power supply RP8 is any one of Sn, SnIn, SnZn and SnO2, RF power supply RP8 is sputtered at room temperature and 0.1Pa-1.5Pa working pressure, and ion source L3 is connected with O2, N2O or CF4 for assisted sputtering to prepare a blocking buffer layer with a thickness of 2nm-70nm; S8, in the chamber CB8, on the said blocking buffer layer, prepare a top electrode: set the power of RF power supply RP9 to 10W-300W, the target cathode is any one of Ag, Au, Cu and Al single metal or alloy target material, or the target cathode is TCO target material, RF power supply RP9 is sputtered at room temperature and 0.1Pa-1.5Pa working pressure to prepare a top electrode with a thickness of 2nm-500nm; S9, use a laminator to package the current substrate to obtain a high-stability inorganic perovskite solar cell, wherein the packaging uses ethylene-vinyl acetate copolymer EVA material, and the EVA has hollow glass beads, and the current substrate is part of the high-stability inorganic perovskite solar cell prepared in the current step.

10. The method of claim 9, wherein the method further comprises: The chamber CB2 and the chamber CB5 are the same chamber, the chamber CB3 and the chamber CB6 are one chamber; the chamber CB4 and the chamber CB8 are one chamber.

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