Zinc and cobalt co-doped niO for trans-perovskite cells X Method for producing a thin film

Abstract

The application discloses a preparation method of a trans-perovskite battery zinc and cobalt co-doped NiOX thin film, and comprises the following steps: S1, selecting a substrate, first cleaning the substrate by using a detergent and deionized water, then sequentially placing the substrate in acetone and anhydrous ethanol for ultrasonic cleaning, and drying the substrate by using a nitrogen gun; S2, cleaning the substrate by using radio frequency plasma superposition pulse negative bias; S3, depositing a NiOX thin film on the surface of ITO by using a direct current / radio frequency coupling reaction sputtering process, and co-depositing metal zinc and metal cobalt on the surface of ITO by using a direct current sputtering process; and S4, after the sputtering is completed, cooling the substrate to room temperature, heating the substrate to a constant temperature, and then cooling the substrate to room temperature again to take out the sample, so that the zinc and cobalt co-doped NiOX thin film is obtained. The doped NiOX thin film prepared by the method has better electrical performance and transmittance, the perovskite thin film prepared on the doped NiOX thin film has stable absorption effect, and the trans-perovskite battery has higher photoelectric conversion efficiency and stability.

Description

Technical Field

[0001] This invention relates to the technical field of novel material solar cells, specifically to a zinc- and cobalt-doped NiO for inverted perovskite solar cells. X Thin film preparation methods. Background Technology

[0002] In recent years, organic-inorganic hybrid perovskite materials have advantages such as good light absorption coefficient, long charge diffusion length, excellent carrier transport performance, and tunable band gap width. These materials can effectively absorb sunlight, efficiently generate photogenerated carriers, and reduce energy loss. Perovskite-based solar cells have attracted widespread attention due to their rapidly improving efficiency, with the conversion efficiency of these cells jumping from the initial 3.8% to 26.1%.

[0003] NiOX is a P-type semiconductor material with advantages such as good transparency, high hole mobility and strong chemical stability. As a hole transport layer material, it can effectively improve the open-circuit voltage of perovskite solar cells. However, the low conductivity of NiOX itself leads to a reduction in the carrier recombination and hole extraction capabilities of perovskite solar cells, resulting in a lower device fill factor and short-circuit current, thus affecting the performance of the cell. Currently, the conductivity of NiOX can be improved through effective doping. Patent 201710094986.7 discloses a method for preparing silver-doped nickel oxide thin films, which involves dissolving nickel nitrate hexahydrate and silver nitrate in an ethylene glycol solution containing diethylamine to prepare a mixed precursor solution of nickel nitrate and silver nitrate, which is then spin-coated onto a substrate and heated at 300°C for 60-80 minutes. Patent 201811227041.9 discloses a lithium-silver co-doped nickel oxide thin film, which involves dissolving Ni(NO3)2·6H2O, LiNO3, and AgNO3 in deionized water by stirring, adjusting the pH to 9.8-10 by adding NaOH solution dropwise, and calcining at 270°C after washing and drying to obtain lithium-silver co-doped nickel oxide nanoparticles. These particles are then dissolved in water and spin-coated into a film. The preparation methods of the doped nickel oxide thin films disclosed in the above patents all adopt the solution method. This method requires high-temperature post-treatment, the preparation process is cumbersome, and the repeatability and controllability of the samples are poor, so it cannot be applied to large-scale industrial production. In addition, the doping element silver is a precious metal, and the application cost is high. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a zinc- and cobalt-doped NiO for inverted perovskite solar cells. X The thin film preparation method does not require high-temperature post-treatment, the process is simple, and the sample repeatability and controllability are good, making it suitable for large-scale industrial production.

[0005] To achieve the above objectives, the present invention provides a method for preparing zinc-cobalt co-doped NiOX thin films for inverted perovskite solar cells, which specifically includes the following steps:

[0006] S1. Select a pre-patterned ITO glass as the substrate with a sheet resistance of 10Ω. First, use detergent and deionized water to ultrasonically clean for 20 minutes. Then, put it into acetone and anhydrous ethanol for ultrasonic cleaning for 15 minutes each. Finally, dry the substrate with a nitrogen gun.

[0007] S2. Place the substrate into a plasma cleaning device and clean the substrate using radio frequency plasma superimposed with a pulsed negative bias voltage.

[0008] S3. Place the cleaned substrate into the vacuum coating chamber and deposit a NiOX thin film on the ITO surface using a DC / RF coupled reactive sputtering process. At the same time, co-deposit metallic zinc and metallic cobalt on the ITO surface using a DC sputtering process.

[0009] S4. After sputtering, wait for the substrate to cool to room temperature, then heat the substrate to 100-200°C and hold it at that temperature for 15-60 minutes. After the substrate cools to room temperature again, break the vacuum and remove the sample to obtain a zinc-cobalt co-doped NiOX thin film.

[0010] As a further preferred embodiment of the above scheme, step S2 uses radio frequency plasma superimposed with a 200V pulsed negative bias voltage to clean the substrate. A plasma cleaning device is used, with Ar gas as the carrier gas. The working pressure of the device chamber is maintained at 2-25Pa. The working power supply is a radio frequency power supply with a power of 100-400W. The Ar gas flow rate is 15-40sccm. The substrate is subjected to a pulsed negative bias voltage of 200V, and the etching cleaning time is 5-30min.

[0011] As a further preferred embodiment of the above scheme, step S3 employs a DC / RF coupled reactive sputtering process to deposit a NiOX thin film on the ITO surface, while simultaneously using a DC sputtering process to co-deposit zinc and cobalt on the ITO surface. A three-target co-sputtering apparatus is used, with sputtering targets being a nickel target, a zinc target, and a cobalt target. The sputtering power supply for the nickel target is a DC and RF coupled power supply, while the sputtering power supplies for the zinc and cobalt targets are both DC power supplies. The sputtering process gas is Ar, the reactive gas is O2, the base vacuum degree of magnetron sputtering is ≤4×10⁻⁴ Pa, the working pressure is 2×10⁻¹ Pa, the Ar flow rate is 30 sccm, and the O2 flow rate is 10 sccm. The sputtering power for the nickel target is 50–80 W for the RF power supply and 80–120 W for the DC power supply, the sputtering power for the zinc target is 50 W for the DC power supply, and the sputtering power for the cobalt target is 30 W for the DC power supply.

[0012] As a further preferred embodiment of the above scheme, step S3 uses a DC / RF coupled reactive sputtering process to deposit a NiOX thin film on the ITO surface, and simultaneously uses a DC sputtering process to co-deposit metallic zinc and metallic cobalt on the ITO surface. During sputtering, the nickel target power supply is turned on first, and after the glow discharge stabilizes, O2 is slowly introduced. After sputtering for 2 minutes, the O2 flow valve is turned off, and the zinc and cobalt target power supplies are turned on at the same time. After sputtering for 30 seconds, the zinc and cobalt target power supplies are turned off, and the O2 flow valve is turned on again. After sputtering for 3 minutes, a zinc and cobalt co-doped NiOX thin film with a thickness of 20-30 nm is obtained.

[0013] A zinc- and cobalt-doped NiO for inverted perovskite solar cells X The thin film preparation process specifically includes the following steps:

[0014] S1. Select a pre-patterned ITO glass as the substrate with a sheet resistance of 10Ω. First, use detergent and deionized water to ultrasonically clean for 20 minutes. Then, put it into acetone and anhydrous ethanol for ultrasonic cleaning for 15 minutes each. Finally, dry the substrate with a nitrogen gun.

[0015] S2. Place the substrate into a plasma cleaning device and clean the substrate using radio frequency plasma superimposed with a pulsed negative bias voltage.

[0016] S3. Place the cleaned substrate into the vacuum coating chamber and deposit a NiOX thin film on the ITO surface using a DC / RF coupled reactive sputtering process. At the same time, co-deposit metallic zinc and metallic cobalt on the ITO surface using a DC sputtering process.

[0017] S4. After sputtering, wait for the substrate to cool to room temperature, then heat the substrate to 100-200°C and hold it at that temperature for 15-60 minutes. After the substrate cools to room temperature again, break the vacuum and remove the sample to obtain a zinc-cobalt co-doped NiOX thin film.

[0018] A zinc- and cobalt-doped NiO for inverted perovskite solar cells X A thin film preparation system comprising the following modules arranged in sequence:

[0019] A substrate selection module is used to select a pre-patterned ITO glass as a substrate with a sheet resistance of 10Ω.

[0020] The initial cleaning module includes a detergent, a deionized water ultrasonic cleaning device, an acetone and an anhydrous ethanol cleaning device, and a nitrogen gun.

[0021] A secondary cleaning module, which includes a radio frequency plasma superimposed pulse negative bias cleaning device;

[0022] A vacuum coating module includes a vacuum coating chamber in which a NiOX thin film is deposited on an ITO surface using a DC / RF coupled reactive sputtering process, and simultaneously zinc and cobalt are co-deposited on the ITO surface using a DC sputtering process.

[0023] The sample forming module includes a room temperature cooling device, a heating device, a temperature control device, and a vacuum breaking device.

[0024] As a further preferred embodiment of the above scheme, the secondary cleaning module uses radio frequency plasma superimposed with a 200V pulsed negative bias voltage to clean the substrate. A plasma cleaning device is used, with Ar gas as the carrier gas. The working pressure of the device chamber is maintained at 2-25Pa. The working power supply is a radio frequency power supply with a power of 100-400W. The Ar gas flow rate is 15-40sccm. The substrate is subjected to a pulsed negative bias voltage of 200V, and the etching cleaning time is 5-30min.

[0025] As a further preferred embodiment of the above scheme, the vacuum coating module deposits a NiOX thin film on the ITO surface using a DC / RF coupled reactive sputtering process, and simultaneously co-deposits zinc and cobalt on the ITO surface using a DC sputtering process. A three-target co-sputtering device is used, with nickel, zinc, and cobalt targets as the sputtering targets. The sputtering power supply for the nickel target is a DC and RF coupled power supply, while the sputtering power supplies for the zinc and cobalt targets are both DC power supplies. The sputtering process gas is Ar, the reactive gas is O2, the base vacuum of the magnetron sputtering is ≤4×10⁻⁴ Pa, the operating pressure is 2×10⁻¹ Pa, the Ar flow rate is 30 sccm, and the O2 flow rate is 10 sccm. The sputtering power for the nickel target is 50–80 W for the RF power supply and 80–120 W for the DC power supply; the sputtering power for the zinc target is 50 W for the DC power supply; and the sputtering power for the cobalt target is 30 W for the DC power supply.

[0026] As a further preferred embodiment of the above scheme, the vacuum coating module uses a DC / RF coupled reactive sputtering process to deposit a NiOX thin film on the ITO surface, and simultaneously uses a DC sputtering process to co-deposit metallic zinc and metallic cobalt on the ITO surface. During sputtering, the nickel target power supply is turned on first, and after the glow discharge stabilizes, O2 is slowly introduced. After sputtering for 2 minutes, the O2 flow valve is turned off, and the zinc and cobalt target power supplies are turned on at the same time. After sputtering for 30 seconds, the zinc and cobalt target power supplies are turned off, and the O2 flow valve is turned on again. After sputtering for 3 minutes, a zinc and cobalt co-doped NiOX thin film with a thickness of 20-30 nm is obtained.

[0027] The present invention provides a method for preparing zinc and cobalt co-doped NiOX thin films for inverted perovskite solar cells, which has the following beneficial effects:

[0028] 1. The present invention provides a method for preparing zinc and cobalt co-doped NiOX thin films for inverted perovskite solar cells. Compared with solution methods for preparing NiOX thin films, the NiOX thin films prepared by reactive magnetron sputtering do not require high-temperature post-treatment, the process is simple, the sample repeatability and controllability are good, and it is suitable for large-scale industrial production.

[0029] 2. The present invention discloses a method for preparing zinc and cobalt co-doped NiOX thin films for inverted perovskite solar cells. The method employs a DC / RF coupled sputtering process to prepare NiOX thin films, which can not only improve the deposition rate of the films but also reduce the internal stress of the NiOX films, ultimately resulting in more dense and uniform films.

[0030] 3. The present invention provides a method for preparing a zinc-cobalt co-doped NiOX thin film for inverted perovskite solar cells. Compared with nickel oxide thin films doped with silver or silver and lithium, nickel oxide thin films doped with zinc and cobalt also have good light transmittance and hole transport capability. At the same time, the use of common metal doping greatly reduces production costs.

[0031] Specific embodiments of the present invention are disclosed in detail with reference to the following description and accompanying drawings, indicating how the principles of the present invention can be adopted. It should be understood that the embodiments of the present invention are not limited in scope as a result, and the embodiments of the present invention include many changes, modifications and equivalents. Attached Figure Description

[0032] Figure 1 This is the XRD pattern of the zinc- and cobalt-doped nickel oxide thin film in Example 1 of the present invention;

[0033] Figure 2 This is the transmission spectrum of the nickel oxide thin film doped with zinc and cobalt in Example 1 of the present invention;

[0034] Figure 3 This is the absorption spectrum of the perovskite film deposited on a zinc- and cobalt-doped nickel oxide film in Example 1 of the present invention. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. However, it should be understood that the specific embodiments described herein are merely illustrative and are not intended to limit the scope of the invention.

[0036] It should be noted that when an element is referred to as "set on" or "provided with" another element, it can be directly on the other element or there may be an intermediate element. When an element is referred to as "connected to" or "connected to" another element, it can be directly connected to the other element or there may be an intermediate element at the same time. "Fixed connection" means fixed connection. There are many ways of fixed connection, which are not within the scope of protection of this document. The terms "vertical", "horizontal", "left", "right" and similar expressions used in this document are only for illustrative purposes and do not represent the only implementation method.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in the specification herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0038] Please refer to the instruction manual appendix. Figure 1-3 This invention provides a zinc- and cobalt-doped NiO for trans-perovskite solar cells. X A first embodiment of the thin film preparation method includes the following steps:

[0039] S1 uses pre-patterned ITO glass as the substrate with a sheet resistance of 10Ω. It is first ultrasonically cleaned with detergent and deionized water for 20 minutes, and then placed in acetone and anhydrous ethanol for ultrasonic cleaning for 15 minutes each. The substrate is then dried with a nitrogen gun.

[0040] S2 places the dried substrate into a plasma cleaning device, using radio frequency plasma superimposed pulses.

[0041] The substrate was cleaned using a negative bias voltage, with argon gas as the carrier gas. The working pressure of the equipment chamber was 2 Pa, the working power supply was an RF power supply with a power of 100 W, the argon gas flow rate was 15 sccm, the substrate was subjected to a pulsed negative bias voltage of 200 V, and the etching and cleaning time was 30 min.

[0042] S3 places the cleaned substrate into the vacuum deposition chamber and deposits NiO on the ITO surface using a DC / RF coupled reactive sputtering process. X Thin films were co-deposited with zinc and cobalt on the ITO surface using a DC sputtering process. A three-target co-sputtering system was used, with nickel, zinc, and cobalt targets as the sputtering targets. The sputtering power supply for the nickel target was a DC and RF coupled power supply, while the sputtering power supplies for the zinc and cobalt targets were both DC power supplies. Argon was used as the sputtering process gas, and oxygen was used as the reactant gas. The base vacuum level of magnetron sputtering was ≤4×10⁻⁶. -4 Pa, working pressure is 2×10 -1The sputtering process was carried out at 30 sccm for argon and 10 sccm for oxygen. The sputtering power for the nickel target was 80 W for RF and 120 W for DC, for the zinc target 50 W for DC, and for the cobalt target 30 W for DC. During sputtering, the nickel target power was turned on first, and after the glow discharge stabilized, oxygen was slowly introduced. After 2 minutes of sputtering, the oxygen flow valve was closed, and the zinc and cobalt target power supplies were simultaneously turned on. After 30 seconds of sputtering, the zinc and cobalt target power supplies were turned off, and the oxygen flow valve was turned on again. After 3 minutes of sputtering, the substrate was allowed to cool to room temperature, then heated to 100°C and held at that temperature for 15 minutes. After the substrate cooled to room temperature again, the vacuum was broken and the sample was removed, yielding a 20 nm thick zinc-cobalt co-doped NiO. X film.

[0043] Table 1. Electrical parameters of the zinc-cobalt co-doped NiOX thin films obtained in Example 1.

[0044] Sample Name <![CDATA[Carrier concentration (cm -3 )]]> Mobility (cm² / Vs) Electrical conductivity (S / cm) Zn:Co:NiOx-1 <![CDATA[2.02×10 16 ]]> <![CDATA[3.9×10 -1 ]]> <![CDATA[1.2×10 -3 ]]> NiOx <![CDATA[1.31×10 16 ]]> <![CDATA[1.3×10 -1 ]]> <![CDATA[3.1×10 -4 ]]>

[0045] Table 1 shows the zinc and cobalt co-doped NiO obtained in Example 1. X The electrical parameters of the thin film show that metal ion doping significantly improves the performance of NiO. X The conductivity of thin films, Figure 1 The image shows the XRD pattern of the zinc- and cobalt-doped nickel oxide film in Example 1, and the image of pure NiO. X The characteristic diffraction peaks of the thin film are the same, indicating that doping does not affect NiO. X The crystal structure changes. Figure 2 The image shows the transmission spectrum of the zinc- and cobalt-doped nickel oxide thin film in Example 1. The average transmittance in the visible light region is close to 85%, indicating its suitability for use in inverted planar perovskite solar cells. Figure 3 This is the absorption spectrum of the perovskite film deposited on a zinc- and cobalt-doped nickel oxide film in Example 1. Figure 3 It can be observed that the absorption peaks of the film are strong from ultraviolet to near-infrared, and the nickel oxide film doped with zinc and cobalt did not reduce the absorption performance of the perovskite film.

[0046] Please refer to the instruction manual appendix. Figure 1-3 This invention provides a zinc- and cobalt-doped NiO for trans-perovskite solar cells. X A second embodiment of the thin film preparation method includes the following steps:

[0047] S1 uses pre-patterned ITO glass as the substrate with a sheet resistance of 10Ω. It is first ultrasonically cleaned with detergent and deionized water for 20 minutes, and then placed in acetone and anhydrous ethanol for ultrasonic cleaning for 15 minutes each. The substrate is then dried with a nitrogen gun.

[0048] S2 places the dried substrate into a plasma cleaning device, using radio frequency plasma superimposed pulses.

[0049] The substrate was cleaned using a negative bias voltage, with argon gas as the carrier gas. The working pressure of the equipment chamber was 2 Pa, the working power supply was an RF power supply with a power of 100 W, the argon gas flow rate was 15 sccm, the substrate was subjected to a pulsed negative bias voltage of 200 V, and the etching and cleaning time was 30 min.

[0050] S3 places the cleaned substrate into the vacuum deposition chamber and deposits NiO on the ITO surface using a DC / RF coupled reactive sputtering process. X Thin films were simultaneously deposited on ITO surfaces using DC sputtering with zinc and cobalt. A three-target co-sputtering system was employed, with nickel, zinc, and cobalt targets as the sputtering targets. The nickel target was powered by a DC and RF coupled power supply, while the zinc and cobalt targets were powered by DC power supplies. Argon was used as the sputtering process gas, and oxygen was used as the reactive gas. The base vacuum level of magnetron sputtering was ≤4×10⁻⁶. -4 Pa, working pressure is 2×10 -1 The sputtering process was carried out at 30 sccm for argon and 10 sccm for oxygen. The sputtering power for the nickel target was 65 W for RF and 100 W for DC; for the zinc target, 50 W for DC; and for the cobalt target, 30 W for DC. During sputtering, the nickel target power was turned on first, and after the glow discharge stabilized, oxygen was slowly introduced. After 2 minutes of sputtering, the oxygen flow valve was closed, and the zinc and cobalt target power supplies were simultaneously turned on. After 30 seconds of sputtering, the zinc and cobalt target power supplies were closed, and the oxygen flow valve was turned on again. After 3 minutes of sputtering, the substrate was allowed to cool to room temperature, then heated to 150°C and held at that temperature for 35 minutes. After the substrate cooled to room temperature again, the vacuum was broken and the sample was removed, yielding a 25 nm thick zinc-cobalt co-doped NiO. X film.

[0051] Table 2. Zinc- and cobalt-doped NiO obtained in Example 2 X Electrical parameters of thin films

[0052] Sample Name <![CDATA[Carrier concentration (cm -3 )]]> Mobility (cm² / Vs) Electrical conductivity (S / cm) Zn:Co:NiOx-1 <![CDATA[1.82×10 16 ]]> <![CDATA[3.2×10 -1 ]]> <![CDATA[6.3×10 -4 ]]> NiOx <![CDATA[1.31×10 16 ]]> <![CDATA[1.3×10 -1 ]]> <![CDATA[3.1×10 -4 ]]>

[0053] Table 2 shows the zinc and cobalt co-doped NiO obtained in Example 2. X The electrical parameters of the thin film show that metal ion doping significantly improves the performance of NiO. X The conductivity of thin films.

[0054] Please refer to the instruction manual appendix. Figure 1-3 This invention provides a zinc- and cobalt-doped NiO for trans-perovskite solar cells. X A third embodiment of the thin film preparation method includes the following steps:

[0055] S1 uses pre-patterned ITO glass as the substrate with a sheet resistance of 10Ω. It is first ultrasonically cleaned with detergent and deionized water for 20 minutes, and then placed in acetone and anhydrous ethanol for ultrasonic cleaning for 15 minutes each. The substrate is then dried with a nitrogen gun.

[0056] S2 places the dried substrate into a plasma cleaning device, using radio frequency plasma superimposed pulses.

[0057] The substrate was cleaned using a negative bias voltage, with argon gas as the carrier gas. The working pressure of the equipment chamber was 2 Pa, the working power supply was an RF power supply with a power of 100 W, the argon gas flow rate was 15 sccm, the substrate was subjected to a pulsed negative bias voltage of 200 V, and the etching and cleaning time was 30 min.

[0058] S3 places the cleaned substrate into the vacuum deposition chamber and deposits NiO on the ITO surface using a DC / RF coupled reactive sputtering process. X Thin films were simultaneously deposited on ITO surfaces using DC sputtering with zinc and cobalt. A three-target co-sputtering system was employed, with nickel, zinc, and cobalt targets as the sputtering targets. The nickel target was powered by a DC and RF coupled power supply, while the zinc and cobalt targets were powered by DC power supplies. Argon was used as the sputtering process gas, and oxygen was used as the reactive gas. The base vacuum level of magnetron sputtering was ≤4×10⁻⁶. -4 Pa, working pressure is 2×10 -1 The sputtering process was carried out at 30 sccm for argon and 10 sccm for oxygen. The sputtering power for the nickel target was 80 W for RF and 120 W for DC, 50 W for DC, and 30 W for DC. During sputtering, the nickel target power was turned on first, and after the glow discharge stabilized, oxygen was slowly introduced. After 2 minutes of sputtering, the oxygen flow valve was closed, and the zinc and cobalt target power supplies were simultaneously turned on. After 30 seconds of sputtering, the zinc and cobalt target power supplies were turned off, and the oxygen flow valve was turned on again. After 3 minutes of sputtering, the substrate was allowed to cool to room temperature, then heated to 200°C and held at that temperature for 60 minutes. After the substrate cooled to room temperature again, the vacuum was broken and the sample was removed, yielding a 30 nm thick zinc-cobalt co-doped NiO. X film.

[0059] Table 3. Electrical parameters of the zinc and cobalt co-doped NiOX thin films obtained in Example 3.

[0060] Sample Name <![CDATA[Carrier concentration (cm -3 )]]> Mobility (cm² / Vs) Electrical conductivity (S / cm) Zn:Co:NiOx-1 <![CDATA[1.91×10 16 ]]> <![CDATA[3.6×10 -1 ]]> <![CDATA[7.5×10 -4 ]]> NiOx <![CDATA[1.31×10 16 ]]> <![CDATA[1.3×10 -1 ]]> <![CDATA[3.1×10 -4 ]]>

[0061] Table 3 shows the zinc and cobalt co-doped NiO obtained in Example 3. X The electrical parameters of the thin film show that metal ion doping significantly improves the performance of NiO. X The conductivity of thin films.

[0062] Fourth embodiment:

[0063] Based on the above embodiments, we provide a zinc-cobalt co-doped NiO for inverted perovskite solar cells. X A thin film preparation system comprising the following modules arranged in sequence:

[0064] A substrate selection module is used to select a pre-patterned ITO glass as a substrate with a sheet resistance of 10Ω.

[0065] The initial cleaning module includes a detergent, a deionized water ultrasonic cleaning device, an acetone and an anhydrous ethanol cleaning device, and a nitrogen gun.

[0066] A secondary cleaning module, which includes a radio frequency plasma superimposed pulse negative bias cleaning device;

[0067] A vacuum coating module includes a vacuum coating chamber in which a NiOX thin film is deposited on an ITO surface using a DC / RF coupled reactive sputtering process, and simultaneously zinc and cobalt are co-deposited on the ITO surface using a DC sputtering process.

[0068] The sample forming module includes a room temperature cooling device, a heating device, a temperature control device, and a vacuum breaking device.

[0069] As a further preferred embodiment of the above scheme, the secondary cleaning module uses radio frequency plasma superimposed with a 200V pulsed negative bias voltage to clean the substrate. A plasma cleaning device is used, with Ar gas as the carrier gas. The working pressure of the device chamber is maintained at 2-25Pa. The working power supply is a radio frequency power supply with a power of 100-400W. The Ar gas flow rate is 15-40sccm. The substrate is subjected to a pulsed negative bias voltage of 200V, and the etching cleaning time is 5-30min.

[0070] As a further preferred embodiment of the above scheme, the vacuum coating module deposits a NiOX thin film on the ITO surface using a DC / RF coupled reactive sputtering process, and simultaneously co-deposits zinc and cobalt on the ITO surface using a DC sputtering process. A three-target co-sputtering device is used, with nickel, zinc, and cobalt targets as the sputtering targets. The sputtering power supply for the nickel target is a DC and RF coupled power supply, while the sputtering power supplies for the zinc and cobalt targets are both DC power supplies. The sputtering process gas is Ar, the reactive gas is O2, the base vacuum of the magnetron sputtering is ≤4×10⁻⁴ Pa, the operating pressure is 2×10⁻¹ Pa, the Ar flow rate is 30 sccm, and the O2 flow rate is 10 sccm. The sputtering power for the nickel target is 50–80 W for the RF power supply and 80–120 W for the DC power supply; the sputtering power for the zinc target is 50 W for the DC power supply; and the sputtering power for the cobalt target is 30 W for the DC power supply.

[0071] As a further preferred embodiment of the above scheme, the vacuum coating module uses a DC / RF coupled reactive sputtering process to deposit a NiOX thin film on the ITO surface, and simultaneously uses a DC sputtering process to co-deposit metallic zinc and metallic cobalt on the ITO surface. During sputtering, the nickel target power supply is turned on first, and after the glow discharge stabilizes, O2 is slowly introduced. After sputtering for 2 minutes, the O2 flow valve is turned off, and the zinc and cobalt target power supplies are turned on at the same time. After sputtering for 30 seconds, the zinc and cobalt target power supplies are turned off, and the O2 flow valve is turned on again. After sputtering for 3 minutes, a zinc and cobalt co-doped NiOX thin film with a thickness of 20-30 nm is obtained.

[0072] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A zinc, cobalt co-doped NiO for a trans -perovskite battery X Method for the production of thin films, characterized in that, The method specifically comprises the following steps: S1, selecting a pre-patterned ITO glass as a substrate, the sheet resistance of which is 10Ω, first cleaning the substrate with a detergent and deionized water for 20 minutes, then sequentially cleaning the substrate with acetone and anhydrous ethanol for 15 minutes each time, and drying the substrate with a nitrogen gun; S2, placing the substrate into a plasma cleaning device, and cleaning the substrate by using a radio frequency plasma superimposed on a pulsed negative bias; S3, the cleaned substrate is put into a vacuum coating chamber, and a direct current / radio frequency coupled reaction sputtering process is used to deposit NiO on the ITO surface X thin film, and a direct current sputtering process is used to co-deposit metal zinc and metal cobalt on the ITO surface; Step S3: Depositing NiO on the ITO surface by using a direct current / radio frequency coupled reaction sputtering process X The metal zinc and the metal cobalt are co-deposited on the ITO surface by using a direct current sputtering process, a three-target co-sputtering device is used, the sputtering targets are a nickel metal target, a zinc metal target and a cobalt metal target, the sputtering power source of the nickel target is a direct current and radio frequency coupled power source, the sputtering power sources of the zinc target and the cobalt target are direct current power sources, the sputtering process gas is Ar, the reaction gas is O2, the base vacuum degree of the magnetron sputtering is ≤4×10 -4 Pa, the working pressure is 2×10 -1 Pa, the Ar flow rate is 30 sccm, the O2 flow rate is 10 sccm, the sputtering power of the nickel target is 50-80 W for the radio frequency power source and 80-120 W for the direct current power source, the sputtering power of the zinc target is 50 W for the direct current power source, and the sputtering power of the cobalt target is 30 W for the direct current power source. Step S3: Depositing NiO on the ITO surface by using a direct current / radio frequency coupled reaction sputtering process X The metal zinc and the metal cobalt are co-deposited on the ITO surface by using a direct current sputtering process, the nickel target power source is turned on first during sputtering, O2 is slowly introduced after the glow is stable, the O2 flow valve is closed after sputtering for 2 min, the zinc target and the cobalt target power sources are turned on, the zinc target and the cobalt target power sources are turned off after sputtering for 30 s, the O2 flow valve is turned on again, and a zinc / cobalt co-doped NiO film with a thickness of 20-30 nm is obtained after sputtering for 3 min X The metal zinc and the metal cobalt are co-deposited on the ITO surface by using a direct current sputtering process, the nickel target power source is turned on first during sputtering, O2 is slowly introduced after the glow is stable, the O2 flow valve is closed after sputtering for 2 min, the zinc target and the cobalt target power sources are turned on, the zinc target and the cobalt target power sources are turned off after sputtering for 30 s, the O2 flow valve is turned on again, and a zinc / cobalt co-doped NiO film with a thickness of 20-30 nm is obtained after sputtering for 3 min S4, after sputtering is completed, the substrate is cooled to room temperature, the substrate is heated to 100-200℃, constant temperature for 15-60 minutes, the substrate is cooled to room temperature again, the vacuum is broken to take out the sample, and zinc and cobalt co-doped NiO is obtained X thin film.

2. A zinc, cobalt co-doped NiO for a trans-fafium cell according to claim 1 X Method for the production of thin films, characterized in that: The step S2 uses a radio frequency plasma superimposed on a pulsed negative bias of 200V to clean the substrate, uses a plasma cleaning device, uses single Ar gas as a carrier gas, keeps the working pressure of the chamber of the device at 2-25Pa, uses a radio frequency power source as a working power source, the power of which is 100-400W, the Ar gas flow is 15-40sccm, the substrate is added with a pulsed negative bias of 200V, and the etching and cleaning time is 5-30min.

3. A zinc, cobalt co-doped NiO for a trans-perovskite battery according to claim 2 X The production system of the production method of the thin film is characterized by comprising: The preparation system comprises the following modules arranged in sequence: A substrate selection module, which is used to select a pre-patterned ITO glass as a substrate, the sheet resistance of which is 10Ω; A primary cleaning module, which comprises a detergent, deionized water ultrasonic cleaning device, acetone, anhydrous ethanol cleaning device and a nitrogen gun; A secondary cleaning module, which comprises a radio frequency plasma superimposed on a pulsed negative bias cleaning device; A vacuum coating module includes a vacuum coating chamber and uses a direct current / radio frequency coupled reaction sputtering process to deposit NiO on an ITO surface X A thin film is simultaneously deposited on the ITO surface using a direct current sputtering process to co-deposit metal zinc and metal cobalt A sample forming module, which comprises a room temperature cooling device, a heating device, a constant temperature device and a vacuum breaking device.

4. The preparation system according to claim 3, characterized in that: The secondary cleaning module uses a radio frequency plasma superimposed on a pulsed negative bias of 200V to clean the substrate, uses a plasma cleaning device, uses single Ar gas as a carrier gas, keeps the working pressure of the chamber of the device at 2-25Pa, uses a radio frequency power source as a working power source, the power of which is 100-400W, the Ar gas flow is 15-40sccm, the substrate is added with a pulsed negative bias of 200V, and the etching and cleaning time is 5-30min.

5. The preparation system according to claim 4, characterized in that: The vacuum coating module adopts a direct current / radio frequency coupling reaction sputtering process to deposit NiO on the ITO surface X Thin film, while using direct current sputtering process in ITO surface co-deposition of metal zinc and metal cobalt, using three target co-sputtering equipment, sputtering target material is nickel metal target, zinc target and cobalt target, wherein the nickel target sputtering power supply is direct current and radio frequency coupling power supply, zinc target and cobalt target sputtering power supply are direct current power supply, sputtering process gas is Ar, reaction gas is O2, the base vacuum degree of magnetron sputtering is less than or equal to 4*10 -4 Pa, working pressure is 2*10 -1 Pa, Ar flow is 30sccm, O2 flow is 10sccm, nickel target sputtering power is radio frequency power supply 50~80W, direct current power supply 80~120W, zinc target sputtering power is direct current power supply 50W, cobalt target sputtering power is direct current power supply 30W.

6. The preparation system according to claim 5, characterized in that: The vacuum coating module adopts a direct current / radio frequency coupling reaction sputtering process to deposit NiO on the ITO surface X The film is co-deposited with metal zinc and metal cobalt on the ITO surface by using a direct current sputtering process, the nickel target power is turned on first during sputtering, O2 is slowly introduced after the glow is stable, the O2 flow valve is closed after sputtering for 2 min, the zinc target and cobalt target powers are turned on, the zinc target and cobalt target powers are turned off after sputtering for 30 s, the O2 flow valve is turned on again, and the zinc and cobalt co-doped NiO with a thickness of 20-30 nm is obtained after sputtering for 3 min X The film is co-deposited with metal zinc and metal cobalt on the ITO surface by using a direct current sputtering process, the nickel target power is turned on first during sputtering, O2 is slowly introduced after the glow is stable, the O2 flow valve is closed after sputtering for 2 min, the zinc target and cobalt target powers are turned on, the zinc target and cobalt target powers are turned off after sputtering for 30 s, the O2 flow valve is turned on again, and the zinc and cobalt co-doped NiO with a thickness of 20-30 nm is obtained after sputtering for 3 min

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