Preparation method for inverted perovskite cell based on co-doped nickel oxide hole transport layer

Abstract

Disclosed in the present invention is a preparation method for an inverted perovskite cell based on a co-doped nickel oxide hole transport layer. The method comprises: a, sequentially using a detergent, deionized water and acetone to perform ultrasonic cleaning on a transparent substrate at 45°C for 25 min; b, using a magnetron sputtering process to obtain a patterned transparent conductive electrode; c, preparing a hole transport layer on the transparent conductive electrode using a co-sputtering method to obtain the hole transport layer having a thickness of 20-40 nm; d, preparing a perovskite absorption layer on the hole transport layer using a co-evaporation method to obtain the perovskite absorption layer having a thickness of 300-600 nm; e, preparing an electron transport layer on the perovskite absorption layer using a spin-coating method to obtain the electron transport layer having a thickness of 60-90 nm; and f, preparing a back electrode on the electron transport layer by means of electron beam evaporation, and performing mask evaporation to obtain the back electrode having a thickness of 90-120 nm. The cell obtained using the preparation method has good stability and high conversion efficiency, involves a simple preparation process, has a low cost, and allows for easy industrial application.

Description

A method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer Technical Field

[0001] The present invention relates to the technical field of perovskite solar cells, and in particular to a method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer. Background Art

[0002] In recent years, organic-inorganic hybrid perovskite materials have advantages such as good absorption coefficient, long charge diffusion length, excellent carrier transport performance, and adjustable band gap width, which enable this material to effectively absorb sunlight, efficiently generate photogenerated carriers while reducing energy loss. The rapid improvement in efficiency of solar cells based on perovskite materials has attracted widespread attention, and the conversion efficiency of its batteries has jumped from the initial 3.8% to 26.1%.

[0003] Compared with the traditional formal structure, the inverse perovskite battery has a negligible hysteresis effect and a lower trap state density at the interface of the perovskite material, which makes the charge transfer smoother. In addition, the flexible device with inverse structure can be prepared at low temperature and has good interface stability. x Inverse perovskite cells with hole transport layers have attracted widespread attention due to their high chemical stability, simple preparation process and low price. X Factors such as weak intrinsic conductivity and poor energy level matching lead to a reduction in the carrier lifetime and hole extraction capability of perovskite batteries, resulting in low fill factor and short-circuit current, thus affecting the overall performance of the battery.

[0004] To this end, we provide a preparation method for an inverse perovskite cell based on a co-doped nickel oxide hole transport layer to solve the above problems. Summary of the Invention

[0005] In response to the problems existing in the above-mentioned prior art, the present invention provides a method for preparing an inverse perovskite battery based on a co-doped nickel oxide hole transport layer. The battery obtained by this preparation method has good stability, high conversion efficiency, simple preparation process, low cost and is easy to industrialize and apply.

[0006] A method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer comprises the following steps:

[0007] a. Ultrasonic cleaning of the transparent substrate with detergent, deionized water, and acetone at 45°C for 25 min each;

[0008] b. Using magnetron sputtering technology, CdSnO4 and ZnSnO4 ceramic targets were selected to deposit CdSnO4 thin film on the substrate surface through a metal mask. The background vacuum of the cavity was 2×10-6 Pa, the RF power is 50~200W, and the working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 40sccm, the thickness is 180~230nm, and then the ZnSnO4 film is deposited. The background vacuum of the cavity is 2×10 -6 Pa, the RF power is 100-200W, and the working pressure is 4×10 -1 Pa, the working gas Ar flow rate is 35 sccm, the thickness is 10 to 25 nm, and a patterned transparent conductive electrode is obtained.

[0009] c. The hole transport layer was prepared on the transparent conductive electrode by co-sputtering method, using Ni, Zn and Co metal targets, and the background vacuum of the cavity was 4×10 -4 Pa, working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 30sccm, the reaction gas O2 flow rate is 10sccm, the Ni target uses an RF power supply with a sputtering power of 60W, the Zn target and the Co target use a DC power supply with sputtering powers of 40W and 30W respectively, and a hole transport layer with a thickness of 20 to 40nm is obtained.

[0010] d. The perovskite absorption layer was prepared on the hole transport layer by co-evaporation method. CsBr, PbI2, FAI and MAI were selected as evaporation sources. The background vacuum of the cavity was 2×10 -4 The evaporation temperature of Pa, FAI is 130℃, the evaporation temperature of MAI is 150℃, the evaporation temperature of PbI2 is 310℃, and the evaporation temperature of CsBr is 420℃. The evaporation rate and film thickness are monitored by a quartz crystal monitor. After the evaporation is completed, a perovskite absorption layer with a thickness of 300-600nm is obtained by heat treatment at 100℃ for 10 minutes.

[0011] e. An electron transport layer was prepared on the perovskite absorption layer by spin coating. A 10 mg / mL PCBM solution in chlorobenzene was first spin-coated on the perovskite surface at 2500 rpm. Then, a 0.5 mg / mL BCP solution in isopropanol was spin-coated on the PCBM surface at 4000 rpm to obtain an electron transport layer with a thickness of 60 to 90 nm.

[0012] f. Electron beam evaporation was used to prepare the back electrode on the electron transport layer. The film materials were metal Cu and Al. The working gas was Ar with a purity of 99.99%. The background vacuum of the cavity was ≤2×10 -4 Pa, working pressure is 1×10 -3 Pa, the electron gun voltage is 7.5Kv, the current is 0.1-0.5A, and the back electrode with a thickness of 90-120nm is obtained by evaporation through a mask plate.

[0013] Furthermore, in the step c, the nickel target power supply is first turned on during sputtering, and O2 is slowly introduced after the glow stabilizes. After sputtering for 2 minutes, the O2 flow valve is closed, and the zinc target and cobalt target power supplies are turned on at the same time. After sputtering for 30 to 60 seconds, the zinc target and cobalt target power supplies are turned off, and the O2 flow valve is opened again, and sputtering is performed for 3 to 5 minutes. After completion of sputtering, the hole transport layer prepared is heat treated at 200°C for 15 minutes.

[0014] Furthermore, in step d, the FAI evaporation source is first turned on with an evaporation rate of 1.55 A / s, then the MAI evaporation source is turned on with an evaporation rate of 1.6 A / s, then the PbI2 evaporation source is turned on with an evaporation rate of 0.90 A / s, and finally the CsBr evaporation source is turned on with an evaporation rate of 0.07 A / s.

[0015] Furthermore, in the step f, metal Cu is evaporated first at an evaporation rate of 10 A / s and a deposition time of 60 to 90 s, and then metal Al is evaporated at an evaporation rate of 10 A / s and a deposition time of 30 s.

[0016] An inverted perovskite cell based on a co-doped nickel oxide hole transport layer, the perovskite cell comprising, from bottom to top, a transparent substrate, a transparent conductive electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a back electrode; the transparent conductive electrode is composed of a low-resistance conductive layer and a high-resistance conductive layer; the hole transport layer is a Zn and Co co-doped NiOx film.

[0017] Furthermore, the transparent substrate is a high-precision, low-iron ultra-clear glass with an iron content of less than 50 parts per million (PPM), resulting in exceptional transparency. The glass substrate has a transmittance exceeding 94% within the wavelength range of 380 to 1100 nm. This transparent substrate maximizes light absorption, enhancing optical performance and delivering exceptional optical results.

[0018] Furthermore, the low-resistance conductive layer is CdSnO4, the high-resistance conductive layer is ZnSnO4, the transparent conductive electrode has a square resistance of ≤10Ω, and an average transmittance in the visible light region of ≥87%.

[0019] Furthermore, the conductivity of the Zn and Co co-doped NiOx film is ≥8×10 -4 S / cm.

[0020] Furthermore, the perovskite absorption layer is Cs x (FA 0.91 MA 0.09 )Pb(I 1-y Br y )3, the x value range is 0.05~0.20, and the y value range is 0.08~0.25.

[0021] Furthermore, the electron transport layer is a composite layer of PCBM and BCP.

[0022] Furthermore, the back electrode is a Cu / Al composite electrode.

[0023] The inverse perovskite cell based on a co-doped nickel oxide hole transport layer of the present invention has the following beneficial effects:

[0024] (1) Compared with traditional transparent conductive electrodes using ITO or FTO, the composite conductive electrode layer using a low-resistance conductive layer CdSnO4 and a high-resistance conductive layer ZnSnO4 can achieve a thinner electrode layer while achieving the same resistivity, resulting in higher transmittance and lower cost. The HOMO energy level of a single conductive layer is much higher than that of the hole transport layer. The addition of a high-resistance conductive layer can form a gradient reduction in the band gap energy level, effectively reducing the interface barrier between the electrode layer and the hole transport layer, and increasing the hole extraction capability.

[0025] (2) Using Zn and Co-doped NiOx film as the hole transport layer can effectively improve the conductivity and transmittance of the film, increase the hole separation efficiency at the interface, and reduce the probability of charge recombination at the interface, which is beneficial to the improvement of the overall performance of the battery.

[0026] (3) The co-evaporation method is used to prepare the perovskite absorption layer. Compared with the traditional solution method, it reduces the anhydrous and oxygen-free preparation environment, reduces the production cost, and simplifies the preparation process. The sample repeatability and controllability are good, which is suitable for large-scale industrial production.

[0027] With reference to the following description and drawings, specific embodiments of the present invention are disclosed in detail, indicating how the principles of the present invention can be adopted. It should be understood that the scope of the embodiments of the present invention is not limited thereby, and the embodiments of the present invention include many changes, modifications and equivalents. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG1 is a schematic diagram of the structure of an inverted perovskite cell based on a co-doped nickel oxide hole transport layer according to the present invention;

[0029] FIG2 is a performance diagram of an inverse perovskite cell prepared in Example 1 of the present invention;

[0030] FIG3 is an EQE diagram of the inverse perovskite cell prepared in Example 1 of the present invention;

[0031] FIG4 is a diagram showing the efficiency of the inverse perovskite cell prepared in Example 1 of the present invention after operating at 85° C. for 600 h. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below through the accompanying drawings and embodiments. However, it should be understood that the specific embodiments described herein are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0033] It should be noted that when an element is referred to as being "disposed on, provided with" another element, it may be directly on the other element or there may also be a central element. When an element is considered to be "connected, connected to" another element, it may be directly connected to the other element or there may be a central element at the same time. "Fixed connection" means a fixed connection. There are many ways of fixed connection, which are not within the scope of protection of this article. The terms "vertical", "horizontal", "left", "right" and similar expressions used in this article are for illustrative purposes only and do not represent the only implementation method.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs. The terms used in the specification are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0035] The solar cell device provided by the present invention operates on the following principle: when sunlight enters the absorption layer from the transparent electrode layer, excitons are generated. The excitons move to the absorption layer / transport layer interface. Under the action of a self-built electric field, electrons and holes separate and reach the cathode and anode respectively through the transport layer, forming a photogenerated current. The schematic diagram of the structure of an inverted perovskite cell based on a co-doped nickel oxide hole transport layer provided by the present invention is shown in Figure 1: 1 is a transparent substrate, 2 is a transparent conductive electrode, 3 is a hole transport layer, 4 is a perovskite absorption layer, 5 is an electron transport layer, 6 is a back electrode, 7 is a low-resistance conductive layer, and 8 is a high-resistance conductive layer. The perovskite cell preparation method is simple and reproducible.

[0036] In order to deepen the understanding of the present invention, the present invention will be further described in detail below with reference to the examples. The examples are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0037] Example 1

[0038] The present invention provides a method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer, comprising the following steps:

[0039] a. Select 20×20 cm low-iron ultra-clear glass as the transparent substrate and ultrasonically clean the transparent substrate with detergent, deionized water, and acetone at 45°C for 25 minutes respectively;

[0040] b. Transfer the cleaned transparent substrate to a vacuum chamber, place a metal mask on the sample surface, select CdSnO4 and ZnSnO4 ceramic targets, and first deposit a CdSnO4 film on the substrate surface. The background vacuum of the chamber is 2×10 -6 Pa, the RF power is 120W, and the working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 40sccm, the sputtering time is 10min, and the thickness is 200nm. Then the ZnSnO4 film is deposited, and the background vacuum of the chamber is 2×10 -6 Pa, the RF power is 150W, and the working pressure is 4×10 -1 Pa, the working gas Ar flow rate is 35 sccm, the sputtering time is 2 min, the thickness is 20 nm, and a patterned transparent conductive electrode is obtained.

[0041] c. The sample was transferred to a vacuum chamber and a hole transport layer was prepared on the transparent conductive electrode by co-sputtering. Ni, Zn and Co metal targets were selected. The background vacuum of the chamber was 4×10 -4 Pa, working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 30sccm, the reaction gas O2 flow rate is 10sccm, the Ni target uses an RF power supply, the sputtering power is 60W, the Zn target and the Co target use a DC power supply, the sputtering powers are 40W and 30W respectively. During sputtering, the nickel target power supply is turned on first, and O2 is slowly introduced after the glow is stable. After sputtering for 2 minutes, the O2 flow valve is closed, and the zinc target and cobalt target power supplies are turned on at the same time. After sputtering for 30 seconds, the zinc target and cobalt target power supplies are turned off, and the O2 flow valve is opened again. Sputtering for 3 minutes, after completion of sputtering, heat treatment is carried out at 200°C for 15 minutes to obtain a hole transport layer with a thickness of 20nm.

[0042] d. The sample was transferred to a vacuum chamber and a perovskite absorption layer was prepared on the hole transport layer by co-evaporation. CsBr, PbI2, FAI and MAI were selected as evaporation sources. The background vacuum of the chamber was 2×10 -4 The evaporation temperature of Pa, FAI is 130℃, the evaporation temperature of MAI is 150℃, the evaporation temperature of PbI2 is 310℃, and the evaporation temperature of CsBr is 420℃. The evaporation rate and film thickness are monitored by a quartz crystal monitor. First, the FAI evaporation source is turned on with an evaporation rate of 1.55A / s, then the MAI evaporation source is turned on with an evaporation rate of 1.6A / s, then the PbI2 evaporation source is turned on with an evaporation rate of 0.90A / s, and finally the CsBr evaporation source is turned on with an evaporation rate of 0.07A / s. After the evaporation is completed, a perovskite absorption layer with a thickness of 450nm is obtained by heat treatment at 100℃ for 10 minutes.

[0043] e. Place the sample at room temperature and atmospheric pressure. First, spin-coat a 10 mg / mL PCBM solution in chlorobenzene on the perovskite layer at 2500 rpm for 40 seconds. Then, spin-coat a 0.5 mg / mL BCP solution in isopropanol on the PCBM surface at 4000 rpm for 20 seconds to obtain an 80 nm thick electron transport layer.

[0044] f. The sample was transferred to a vacuum chamber and a back electrode was prepared on the electron transport layer by electron beam evaporation. The film materials were metal Cu and Al. The working gas was 99.99% pure Ar. The background vacuum of the chamber was 1×10 -4 Pa, working pressure is 1×10 -3 Pa, the electron gun voltage was 7.5 kV, the current was 0.3 A, a mask was placed on the sample surface, and metal Cu was evaporated first at an evaporation rate of 10 A / s and a deposition time of 70 seconds. Then metal Al was evaporated at an evaporation rate of 10 A / s and a deposition time of 30 seconds to obtain a back electrode with a thickness of 100 nm. This resulted in an inverse perovskite cell based on a co-doped nickel oxide hole transport layer.

[0045] Combining Figures 2 to 4, we can see that the open circuit voltage of the battery is 1.02V and the short circuit current is 23.22mA / cm 2 , the fill factor is 79.2%, and the short-circuit current obtained by integrating the EQE spectrum is 23.12 mA / cm 2 , which is similar to the JV test results. After aging the sample at 85℃ for 600h, the conversion efficiency is still 94.5% of the initial efficiency.

[0046] Example 2

[0047] The present invention provides a method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer, comprising the following steps:

[0048] a. Select 20×20 cm low-iron ultra-clear glass as the transparent substrate and ultrasonically clean the transparent substrate with detergent, deionized water, and acetone at 45°C for 25 minutes respectively;

[0049] b. Transfer the cleaned transparent substrate to a vacuum chamber, place a metal mask on the sample surface, select CdSnO4 and ZnSnO4 ceramic targets, and first deposit a CdSnO4 film on the substrate surface. The background vacuum of the chamber is 2×10 -6 Pa, the RF power is 50W, and the working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 40sccm, the sputtering time is 10min, and the thickness is 180nm. Then the ZnSnO4 film is deposited, and the background vacuum of the chamber is 2×10 -6Pa, the RF power is 100W, and the working pressure is 4×10 -1 Pa, the working gas Ar flow rate is 35 sccm, the sputtering time is 2 min, the thickness is 10 nm, and a patterned transparent conductive electrode is obtained.

[0050] c. The sample was transferred to a vacuum chamber and a hole transport layer was prepared on the transparent conductive electrode by co-sputtering. Ni, Zn and Co metal targets were selected. The background vacuum of the chamber was 4×10 -4 Pa, working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 30sccm, the reaction gas O2 flow rate is 10sccm, the Ni target uses an RF power supply, the sputtering power is 60W, the Zn target and the Co target use a DC power supply, the sputtering powers are 40W and 30W respectively. During sputtering, the nickel target power supply is turned on first, and O2 is slowly introduced after the glow is stable. After sputtering for 2 minutes, the O2 flow valve is closed, and the zinc target and cobalt target power supplies are turned on at the same time. After sputtering for 40 seconds, the zinc target and cobalt target power supplies are turned off, and the O2 flow valve is opened again. Sputtering for 4 minutes, after sputtering is completed, heat treatment is performed at 200°C for 15 minutes to obtain a hole transport layer with a thickness of 30nm.

[0051] d. The sample was transferred to a vacuum chamber and a perovskite absorption layer was prepared on the hole transport layer by co-evaporation. CsBr, PbI2, FAI and MAI were selected as evaporation sources. The background vacuum of the chamber was 2×10 -4 The evaporation temperature of Pa, FAI is 130℃, the evaporation temperature of MAI is 150℃, the evaporation temperature of PbI2 is 310℃, and the evaporation temperature of CsBr is 420℃. The evaporation rate and film thickness are monitored by a quartz crystal monitor. First, the FAI evaporation source is turned on with an evaporation rate of 1.55A / s, then the MAI evaporation source is turned on with an evaporation rate of 1.6A / s, then the PbI2 evaporation source is turned on with an evaporation rate of 0.90A / s, and finally the CsBr evaporation source is turned on with an evaporation rate of 0.07A / s. After the evaporation is completed, a perovskite absorption layer with a thickness of 300nm is obtained by heat treatment at 100℃ for 10min.

[0052] e. Place the sample at room temperature and atmospheric pressure. First, spin-coat a 10 mg / mL PCBM solution in chlorobenzene on the perovskite layer at 2500 rpm for 30 seconds. Then, spin-coat a 0.5 mg / mL BCP solution in isopropanol on the PCBM surface at 4000 rpm for 10 seconds to obtain a 60 nm thick electron transport layer.

[0053] f. The sample was transferred to a vacuum chamber and a back electrode was prepared on the electron transport layer by electron beam evaporation. The film materials were metal Cu and Al. The working gas was 99.99% pure Ar. The background vacuum of the chamber was 1×10 -4 Pa, working pressure is 1×10 -3 Pa, the electron gun voltage was 7.5 kV, the current was 0.3 A, a mask was placed on the sample surface, and metal Cu was evaporated first at an evaporation rate of 10 A / s and a deposition time of 60 seconds. Then metal Al was evaporated at an evaporation rate of 10 A / s and a deposition time of 30 seconds to obtain a back electrode with a thickness of 90 nm. This resulted in an inverse perovskite cell based on a co-doped nickel oxide hole transport layer.

[0054] Example 3

[0055] The present invention provides a method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer, comprising the following steps:

[0056] a. Select 20×20 cm low-iron ultra-clear glass as the transparent substrate and ultrasonically clean the transparent substrate with detergent, deionized water, and acetone at 45°C for 25 minutes respectively;

[0057] b. Transfer the cleaned transparent substrate to a vacuum chamber, place a metal mask on the sample surface, select CdSnO4 and ZnSnO4 ceramic targets, and first deposit a CdSnO4 film on the substrate surface. The background vacuum of the chamber is 2×10 -6 Pa, the RF power is 200W, and the working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 40sccm, the sputtering time is 10min, and the thickness is 230nm. Then the ZnSnO4 film is deposited, and the background vacuum of the chamber is 2×10 -6 Pa, the RF power is 200W, and the working pressure is 4×10 -1 Pa, the working gas Ar flow rate is 35 sccm, the sputtering time is 2 min, the thickness is 25 nm, and a patterned transparent conductive electrode is obtained.

[0058] c. The sample was transferred to a vacuum chamber and a hole transport layer was prepared on the transparent conductive electrode by co-sputtering. Ni, Zn and Co metal targets were selected. The background vacuum of the chamber was 4×10 -4 Pa, working pressure is 2×10 -1Pa, the working gas Ar flow rate is 30sccm, the reaction gas O2 flow rate is 10sccm, the Ni target uses an RF power supply, the sputtering power is 60W, the Zn target and the Co target use a DC power supply, the sputtering powers are 40W and 30W respectively. During sputtering, the nickel target power supply is turned on first, and O2 is slowly introduced after the glow is stable. After sputtering for 2 minutes, the O2 flow valve is closed, and the zinc target and cobalt target power supplies are turned on at the same time. After sputtering for 60 seconds, the zinc target and cobalt target power supplies are turned off, and the O2 flow valve is opened again. Sputtering for 5 minutes, after sputtering is completed, heat treatment is performed at 200°C for 15 minutes to obtain a hole transport layer with a thickness of 40nm.

[0059] d. The sample was transferred to a vacuum chamber and a perovskite absorption layer was prepared on the hole transport layer by co-evaporation. CsBr, PbI2, FAI and MAI were selected as evaporation sources. The background vacuum of the chamber was 2×10 -4 The evaporation temperature of Pa, FAI is 130℃, the evaporation temperature of MAI is 150℃, the evaporation temperature of PbI2 is 310℃, and the evaporation temperature of CsBr is 420℃. The evaporation rate and film thickness are monitored by a quartz crystal monitor. First, the FAI evaporation source is turned on with an evaporation rate of 1.55A / s, then the MAI evaporation source is turned on with an evaporation rate of 1.6A / s, then the PbI2 evaporation source is turned on with an evaporation rate of 0.90A / s, and finally the CsBr evaporation source is turned on with an evaporation rate of 0.07A / s. After the evaporation is completed, a perovskite absorption layer with a thickness of 600nm is obtained by heat treatment at 100℃ for 10min.

[0060] e. Place the sample at room temperature and atmospheric pressure. First, spin-coat a 10 mg / mL PCBM solution in chlorobenzene on the perovskite layer at 2500 rpm for 50 seconds. Then, spin-coat a 0.5 mg / mL BCP solution in isopropanol on the PCBM surface at 4000 rpm for 25 seconds to obtain a 90 nm thick electron transport layer.

[0061] f. The sample was transferred to a vacuum chamber and a back electrode was prepared on the electron transport layer by electron beam evaporation. The film materials were metal Cu and Al. The working gas was 99.99% pure Ar. The background vacuum of the chamber was 1×10 -4 Pa, working pressure is 1×10 -3 Pa, the electron gun voltage was 7.5 kV, the current was 0.3 A, a mask was placed on the sample surface, and metal Cu was evaporated first at an evaporation rate of 10 A / s and a deposition time of 85 seconds. Then metal Al was evaporated at an evaporation rate of 10 A / s and a deposition time of 35 seconds to obtain a back electrode with a thickness of 120 nm. This resulted in an inverse perovskite cell based on a co-doped nickel oxide hole transport layer.

[0062] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any person skilled in the art can, without departing from the scope of the technical solution of the present invention, utilize the methods and technical contents disclosed above to make many possible changes and modifications to the technical solution of the present invention, or modify it into an equivalent embodiment with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change, and modification of the above embodiments made in accordance with the technical essence of the present invention without departing from the content of the technical solution of the present invention shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer, characterized in that: include: a. ultrasonically clean the transparent substrate with detergent, deionized water and acetone at 45°C for 25 min respectively; b. A patterned transparent conductive electrode obtained by magnetron sputtering process; c. A hole transport layer is prepared on the transparent conductive electrode by a co-sputtering method to obtain a hole transport layer with a thickness of 20 to 40 nm; d. A perovskite absorption layer is prepared on the hole transport layer by a co-evaporation method to obtain a perovskite absorption layer with a thickness of 300 to 600 nm; e. The electron transport layer was prepared on the perovskite absorption layer by spin coating. A 10 mg / mL PCBM solution in chlorobenzene was first spin coated on the surface of the perovskite layer at a speed of 2500 rpm, and then a 0.5 mg / mL BCP solution in isopropanol was spin coated on the PCBM surface at a speed of 4000 rpm to obtain an electron transport layer with a thickness of 60 to 90 nm. f. The back electrode was prepared on the electron transport layer by electron beam evaporation. The film materials were metal Cu and Al. The working gas was Ar with a purity of 99.99%. The background vacuum of the cavity was ≤2×10 -4 Pa, working pressure is 1×10 -3 Pa, the electron gun voltage is 7.5Kv, the current is 0.1-0.5A, and the back electrode with a thickness of 90-120nm is obtained by evaporation through a mask.

2. According to claim 1, a method for preparing an inverse perovskite cell based on a co-doped nickel oxide hole transport layer, characterized in that: The process of the magnetron sputtering process in step b is as follows: CdSnO4 and ZnSnO4 ceramic targets were selected to deposit CdSnO4 thin film on the substrate surface through a metal mask. The background vacuum of the cavity was 2×10 -6 Pa, the RF power is 50-200W, and the working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 40sccm, the thickness is 180-230nm, and then the ZnSnO4 film is deposited. The background vacuum of the chamber is 2×10 -6 Pa, the RF power is 100-200W, and the working pressure is 4×10 -1 Pa, the working gas Ar flow rate is 35sccm, the thickness is 10-25nm, and the obtained patterned transparent conductive electrode.

3. The method for preparing a trans-perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 2, characterized in that: The process of the co-sputtering method in step c is as follows: Ni, Zn and Co metal targets were selected, and the background vacuum of the chamber was 4×10 -4 Pa, working pressure is 2×10 -1 Pa, the working gas Ar flow rate is 30sccm, the reaction gas O2 flow rate is 10sccm, the Ni target uses an RF power supply with a sputtering power of 60W, the Zn target and the Co target use a DC power supply with sputtering powers of 40W and 30W respectively, and a hole transport layer with a thickness of 20-40nm is obtained.

4. The method for preparing a trans-perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 3, characterized in that: The process of preparing the perovskite absorption layer on the hole transport layer by co-evaporation in step d is as follows: CsBr, PbI2, FAI and MAI were selected as evaporation sources, and the background vacuum of the chamber was 2×10 -4 The evaporation temperature of Pa, FAI is 130℃, the evaporation temperature of MAI is 150℃, the evaporation temperature of PbI2 is 310℃, and the evaporation temperature of CsBr is 420℃. The evaporation rate and film thickness are monitored by a quartz crystal monitor. After the evaporation is completed, a perovskite absorption layer with a thickness of 300-600nm is obtained by heat treatment at 100℃ for 10 minutes.

5. The method for preparing a trans-perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 4, characterized in that: In the step c, the nickel target power supply is first turned on during sputtering, and O2 is slowly introduced after the glow is stable. After sputtering for 2 minutes, the O2 flow valve is closed, and the zinc target and cobalt target power supplies are turned on at the same time. After sputtering for 30 to 60 seconds, the zinc target and cobalt target power supplies are turned off, and the O2 flow valve is turned on again, and sputtering is performed for 3 to 5 minutes. After the sputtering is completed, the prepared hole transport layer is heat treated at 200° C. for 15 minutes; In the step d, the FAI evaporation source is first turned on at an evaporation rate of 1.55 A / s, the MAI evaporation source is then turned on at an evaporation rate of 1.6 A / s, the PbI2 evaporation source is then turned on at an evaporation rate of 0.90 A / s, and finally the CsBr evaporation source is turned on at an evaporation rate of 0.07 A / s; In the step f, metal Cu is evaporated first, with an evaporation rate of 10 A / s and a deposition time of 60 to 90 s, and then metal Al is evaporated, with an evaporation rate of 10 A / s and a deposition time of 30 s.

6. The inverse perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 5, characterized in that: The perovskite cell comprises, from bottom to top, a transparent substrate, a transparent conductive electrode, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a back electrode; the transparent conductive electrode is composed of a low-resistance conductive layer and a high-resistance conductive layer; the hole transport layer is a Zn and Co co-doped NiOx film.

7. The inverse perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 6, characterized in that: The low-resistance conductive layer is CdSnO4, the high-resistance conductive layer is ZnSnO4, the square resistance of the transparent conductive electrode is ≤10Ω, and the average transmittance in the visible light region is ≥87%.

8. The inverse perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 7, characterized in that: The transparent substrate is low-iron ultra-white glass, the iron content is ≤50PPM, and the transmittance of the substrate is ≥94% within the range of 380-1100nm.

9. The inverse perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 8, characterized in that: The conductivity of the Zn and Co co-doped NiOx film is ≥8×10 -4 S / cm, the electron transport layer is a composite layer of PCBM and BCP, and the back electrode is a composite electrode of Cu / Al.

10. The inverse perovskite cell based on a co-doped nickel oxide hole transport layer according to claim 8, characterized in that: The perovskite absorption layer is Cs x (FA 0.91 MA 0.09 )Pb(I 1-y Br y )3, the x value range is 0.05~0.20, and the y value range is 0.08~0.25.

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