Method for preparing perovskite solar cell, and perovskite solar cell

Abstract

Provided in the present application are a perovskite solar cell and a preparation method therefor. Along the propagation path of light, the perovskite solar cell can be divided into a substrate, a transparent conductive layer, a hole transport layer, a light absorption layer, an electron transport layer, a hole blocking layer and a back electrode layer from bottom to top, wherein the hole transport layer is nickel oxide having a single or laminated structure prepared by means of a radio frequency magnetron sputtering method, a smooth and compact film is formed, and the hole transport layer has a uniform grain size and is tightly bonded to a substrate. The present invention can achieve extensive assembly-line production of hole transport layers in perovskite solar cells, overcomes limitations of solution methods such as a spin coating method on size, is simple in terms of process operation, high in terms of repeatability and suitable for large-scale production, and can greatly improve production efficiency.

Description

A method for preparing a perovskite solar cell and a perovskite solar cell Technical Field

[0001] The present application relates to the field of thin-film solar cell material preparation, and in particular to a method for preparing a perovskite solar cell and a perovskite solar cell. Background Art

[0002] Global warming and energy crisis are urgent problems that need to be solved by mankind. The development of renewable energy, especially solar energy, has become the development trend of the current energy industry. After years of continuous optimization, solar cells have developed into the third generation of new thin-film solar cells based on organic, dye-sensitized and perovskite. Among them, perovskite solar cells (PSCs) have the characteristics of low cost, simple process, and easy preparation on flexible substrates. They have become a hot spot in the field of photovoltaic devices and are considered to be one of the most promising photovoltaic technologies. In May 2023, the small-sized PSCs developed by the Institute of Semiconductors of the Chinese Academy of Sciences achieved a photoelectric conversion efficiency of 26%, setting a new world record. In March 2023, the Korea Institute of Chemical Technology successfully prepared a PSC with an active area of ​​more than 209 cm 2 , a large-area, high-efficiency perovskite battery module with a photoelectric conversion efficiency of 19.91%.

[0003] Based on the light propagation path, current PSC structures can be categorized as either normal (nip) or inverted (pin). While normal PSCs have slightly higher efficiency, inverted PSCs exhibit a smaller hysteresis effect and have attracted considerable research attention. The typical structure of an inverted PSC consists of an anode, a hole transport layer (HTL), a perovskite absorber layer, an electron transport layer, and a cathode. The primary function of the hole transport layer (HTL) is to extract holes generated by light excitation from the perovskite layer and transport them to the electrode. Its energy level must match that of the perovskite layer and the electrode to facilitate hole collection. It also inhibits electron-hole recombination, thereby reducing energy losses at the interface between the electrode and perovskite layer. Excellent hole transport materials require excellent hole transport properties, stability, simple preparation processes, and good light transmittance. The HTL significantly influences perovskite crystal growth, device stability, and cost. Therefore, by manipulating the effect of the hole transport material on the perovskite layer, the stability and photoelectric conversion efficiency of inverted devices can be effectively improved.

[0004] Common hole transport materials include polystyrene sulfonate (PEDOT:PSS), poly(bis(4-phenyl)(2, 4, 6-trimethylphenyl)amine) (PTAA), poly(3-(4-carboxybutyl)thiophene) (P3CT), and nickel oxide. PEDOT:PSS offers advantages such as high conductivity and transmittance, but its inherent hygroscopicity leads to poor stability in PSCs. PTAA can be prepared at low temperatures, but its price, roughly 50 times that of gold, hinders large-scale commercialization. P3CT suffers from the inherent disadvantage of conjugated polyelectrolyte aggregation, which affects the film quality of the hole transport layer and the crystallization of the perovskite, resulting in poor device performance.

[0005] Summary of the Invention

[0006] In view of this, it is necessary to provide a method that can improve the hole concentration and transmittance, which is more conducive to the preparation of high-efficiency perovskite solar cells, in order to address the problems of the existing technology in the film formation quality of the hole transport layer and the crystallization of the perovskite, which leads to poor device performance.

[0007] To solve the above problems, this application adopts the following technical solutions:

[0008] One of the purposes of this application is to provide a method for preparing a perovskite solar cell, comprising the following steps:

[0009] providing a substrate;

[0010] preparing a transparent conductive layer on the upper surface of the substrate;

[0011] Depositing a hole transport layer on the transparent conductive layer by radio frequency magnetron sputtering, wherein the hole transport layer is nickel oxide having a single or laminated structure;

[0012] preparing a perovskite absorption layer on the upper surface of the hole transport layer;

[0013] preparing an electron transport layer on the upper surface of the perovskite absorption layer;

[0014] preparing a hole blocking layer on the upper surface of the electron transport layer;

[0015] A back electrode layer is prepared on the upper surface of the hole blocking layer.

[0016] In some embodiments, the step of providing a substrate specifically includes the following steps:

[0017] The substrate was rinsed with deionized water. After cleaning, the substrate was placed in an ultrasonic cleaner and then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol for 30 minutes in sequence. The substrate was then transferred to a dust-free shed and residual liquid on the substrate surface was removed with high-pressure pure nitrogen.

[0018] In some embodiments, the substrate comprises soda-lime glass, stainless steel foil, titanium foil, or PET.

[0019] In some embodiments, the step of preparing a transparent conductive layer on the upper surface of the substrate specifically includes the following steps: placing the substrate into a magnetron sputtering chamber and evacuating the vacuum to a specified pressure, filling the chamber with an argon-oxygen mixture for magnetron sputtering to obtain the transparent conductive layer, wherein the volume of O2 in the argon-oxygen mixture is 0≤O2≤10%, and the remainder is Ar, the sputtering temperature is 20~150°C, the sputtering thickness is 50~150 nm, and the transmittance of the transparent conductive layer is greater than 90%, and the square resistance is less than 20Ω.

[0020] In some embodiments, the step of depositing a hole transport layer on the transparent conductive layer by using a radio frequency magnetron sputtering method specifically includes the following steps: placing a sample with a transparent conductive layer prepared on the upper surface of the substrate into a magnetron sputtering chamber and evacuating the vacuum to a specified pressure, sequentially filling the chamber with an argon-oxygen mixture and an argon-nitrogen mixture for radio frequency magnetron sputtering, and annealing the sample after sputtering to obtain the hole transport layer, wherein: the sputtering temperature is 20~300°C, the sputtering thickness is 10~30 nm, the annealing temperature is 100~500°C, the thickness of the hole transport layer is 20 nm, and the transmittance is higher than 80%.

[0021] In some embodiments, the target material in the RF magnetron sputtering is a nickel oxide ceramic target material of 590 mm*90 mm*5 mm and a purity of 99.99%, and the distance from the target to the substrate is 80 mm; if the nickel oxide prepared by filling an argon-oxygen mixture is called A, and the nickel oxide prepared by filling an argon-nitrogen mixture is called B, then the prepared hole transport layer structure can be but is not limited to AA, BB, AABB, ABAB, BABA, BBAA, wherein the O2 content in the argon-oxygen mixture is 0≤O2≤5%, and the O2 content in the argon-nitrogen mixture is 0≤O2≤20%.

[0022] In some embodiments, the step of preparing a perovskite absorption layer on the upper surface of the hole transport layer specifically includes the following steps: transferring the sample of the hole transport layer deposited on the transparent conductive layer into a glove box, preparing a perovskite layer with a thickness of 500-600 nm by a solution method, and annealing at 90-110 ° C for 25-40 min, wherein the perovskite absorption layer is a halide perovskite with a crystal structure of ABX3, wherein A is an organic cation or an inorganic cation, and B is a divalent metal ion Pb 2+ or Sn 2+ ; X is a halogen ion I, Br or Cl.

[0023] In some embodiments, the step of preparing an electron transport layer on the upper surface of the perovskite absorption layer specifically includes the following steps: transferring the sample obtained by preparing the perovskite absorption layer on the upper surface of the hole transport layer to a rotary evaporator, and evaporating a 20-40 nm thick electron transport layer, wherein the electron transport layer can be one of C60, PCBM or SnO2.

[0024] In some embodiments, the step of preparing a hole blocking layer on the upper surface of the electron transport layer specifically includes the following steps: transferring the sample of the electron transport layer prepared on the upper surface of the perovskite absorption layer to a rotary evaporator, and evaporating 5-10 nm thick BCP as a hole blocking layer.

[0025] In some embodiments, the step of preparing a back electrode layer on the upper surface of the hole blocking layer specifically includes the following steps: transferring the sample on which the hole blocking layer is prepared on the upper surface of the electron transport layer to a rotary evaporator, and evaporating a 100-150 nm thick back electrode layer, wherein the back electrode layer can be but is not limited to Au, Ag, Cu, or Al.

[0026] The second purpose of the present application is to provide a perovskite solar cell, which can be divided into a substrate, a transparent conductive layer, a hole transport layer, a light absorption layer, an electron transport layer, a hole blocking layer, and a back electrode layer from bottom to top, wherein the hole transport layer is a single or stacked structure of nickel oxide prepared by radio frequency magnetron sputtering.

[0027] This application adopts the above technical solution, and its beneficial effects are as follows:

[0028] The perovskite solar cell and its preparation method provided in the present application can be divided into a substrate, a transparent conductive layer, a hole transport layer, a light absorption layer, an electron transport layer, a hole blocking layer, and a back electrode layer from bottom to top according to the propagation path of light; the hole transport layer is a single or stacked structure of nickel oxide prepared by radio frequency magnetron sputtering, the film layer is flat and dense, the grain size is uniform, and it is tightly bonded to the substrate; the present invention can realize large-area assembly line production of the hole transport layer in the perovskite solar cell, overcoming the size limitations of solution methods such as spin coating, the process operation is simple, the repeatability is high, it is suitable for large-scale production, and can greatly improve production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments of the present application or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0030] FIG1 is a flow chart of the steps of a method for preparing a perovskite solar cell provided in an embodiment of the present application;

[0031] FIG2 is a schematic structural diagram of a perovskite solar cell provided in an embodiment of the present application;

[0032] FIG3 is a comparison diagram of the JV curves of sputtered nickel oxide and spin-coated nickel oxide-based perovskite solar cells provided in Example 1 of the present application.

[0033] DETAILED DESCRIPTION

[0034] The following describes in detail embodiments of the present application, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present application, and should not be construed as limiting the present application.

[0035] In the description of this application, it should be understood that the terms "upper", "lower", "horizontal", "inside", "outside", etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing this application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on this application.

[0036] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. Throughout the description of this application, "plurality" means two or more, unless otherwise specifically defined.

[0037] In order to make the purpose, technical solutions and advantages of this application more clear, this application is further described in detail below with reference to the accompanying drawings and embodiments.

[0038] Please refer to FIG1 . The method for preparing a perovskite solar cell provided in this embodiment includes the following steps S110 to S150 . The specific implementation of each step is described in detail below.

[0039] Step S110: providing a substrate.

[0040] In this embodiment, the substrate includes soda-lime glass, stainless steel foil, titanium foil, and PET.

[0041] Specifically, the substrate is first rinsed with deionized water, and a cleaning agent is used for auxiliary cleaning during this process. The cleaning time is longer than 10 minutes. After cleaning, the substrate is placed in an ultrasonic cleaning machine, and then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol for 30 minutes in sequence. After the ultrasonic cleaning is completed, the substrate is transferred to a dust-free shed and the residual liquid on the surface of the substrate is removed with high-pressure pure nitrogen.

[0042] Step S120: preparing a transparent conductive layer on the upper surface of the substrate.

[0043] In this embodiment, the step of preparing a transparent conductive layer on the upper surface of the substrate specifically includes the following steps: placing the substrate into a magnetron sputtering chamber and evacuating the vacuum to a specified pressure, filling the chamber with an argon-oxygen mixture and performing magnetron sputtering to obtain the transparent conductive layer, wherein the volume of O2 in the argon-oxygen mixture is 0≤O2≤10%, and the remainder is Ar, the sputtering temperature is 20~150°C, the sputtering thickness is 50~150 nm, and the transmittance of the transparent conductive layer is greater than 90%, and the square resistance is less than 20Ω.

[0044] Step S130: depositing a hole transport layer on the transparent conductive layer by radio frequency magnetron sputtering, wherein the hole transport layer is nickel oxide with a single or laminated structure.

[0045] In this embodiment, the step of depositing a hole transport layer on the transparent conductive layer by using a radio frequency magnetron sputtering method specifically includes the following steps: placing a sample with a transparent conductive layer prepared on the upper surface of the substrate into a magnetron sputtering chamber and evacuating the vacuum to a specified pressure, sequentially filling the chamber with an argon-oxygen mixture and an argon-nitrogen mixture for radio frequency magnetron sputtering, and annealing the sample after sputtering to obtain the hole transport layer, wherein: the sputtering temperature is 20~300°C, the sputtering thickness is 10~30 nm, the annealing temperature is 100~500°C, the thickness of the hole transport layer is 20 nm, and the transmittance is higher than 80%.

[0046] Furthermore, in the RF magnetron sputtering, the target material is a nickel oxide ceramic target material of 590 mm*90 mm*5 mm and a purity of 99.99%, and the distance from the target material to the substrate is 80 mm; if the nickel oxide prepared by filling an argon-oxygen mixture is called A, and the nickel oxide prepared by filling an argon-nitrogen mixture is called B, then the prepared hole transport layer structure can be but is not limited to AA, BB, AABB, ABAB, BABA, BBAA, wherein the O2 content in the argon-oxygen mixture is 0≤O2≤5%, and the O2 content in the argon-nitrogen mixture is 0≤O2≤20%.

[0047] Nickel oxide is a chemically stable direct-bandgap semiconductor material with a wide bandgap and good light transmittance in the 400-800 nm wavelength range. As an inorganic material, nickel oxide has higher photothermal stability, which is more conducive to optimizing the stability of perovskite solar cells. Nickel oxide has a wide and tunable bandgap, and its energy levels closely match those of perovskites, making it suitable as a hole transport material in the commercialization of perovskite solar cells.

[0048] In addition, the magnetron sputtering method used in this embodiment is low-cost and simple to operate, which is more conducive to commercial production and has better application prospects.

[0049] Step S140: preparing a perovskite absorption layer on the upper surface of the hole transport layer.

[0050] In this embodiment, the step of preparing a perovskite absorption layer on the upper surface of the hole transport layer specifically includes the following steps: transferring the sample of the hole transport layer deposited on the transparent conductive layer into a glove box, preparing a perovskite layer with a thickness of 500-600 nm by a solution method, and annealing at 90-110 ° C for 25-40 min, wherein the perovskite absorption layer is a halide perovskite with a crystal structure of ABX3, wherein A is an organic cation or an inorganic cation, and B is a divalent metal ion Pb 2+ or Sn 2+ ; X is a halogen ion I, Br or Cl.

[0051] Step S150: preparing an electron transport layer on the upper surface of the perovskite absorption layer.

[0052] In this embodiment, the step of preparing an electron transport layer on the upper surface of the perovskite absorption layer specifically includes the following steps: transferring the sample obtained by preparing the perovskite absorption layer on the upper surface of the hole transport layer to a rotary evaporator, and evaporating a 20-40 nm thick electron transport layer, wherein the electron transport layer can be one of C60, PCBM or SnO2.

[0053] Step S160: preparing a hole blocking layer on the upper surface of the electron transport layer.

[0054] In this embodiment, the step of preparing a hole blocking layer on the upper surface of the electron transport layer specifically includes the following steps: transferring the sample on which the electron transport layer is prepared on the upper surface of the perovskite absorption layer to a rotary evaporator, and evaporating 5-10 nm thick BCP as the hole blocking layer.

[0055] Step S170: preparing a back electrode layer on the upper surface of the hole blocking layer.

[0056] In this embodiment, the step of preparing a back electrode layer on the upper surface of the hole blocking layer specifically includes the following steps: transferring the sample on which the hole blocking layer is prepared on the upper surface of the electron transport layer to a rotary evaporator, and evaporating a 100-150 nm thick back electrode layer, wherein the back electrode layer may be, but is not limited to, Au, Ag, Cu, or Al.

[0057] The preparation method of the perovskite solar cell provided in the above embodiment of the present application uses radio frequency magnetron sputtering to deposit a single or stacked structure of nickel oxide hole transport layer, which not only increases the carrier concentration of the nickel oxide hole transport layer, promotes carrier transport, but also improves the transmittance; the magnetron sputtering process not only improves the consistency and repeatability of the nickel oxide hole transport layer, but also facilitates large-area assembly line production.

[0058] Please refer to Figure 2. The present application also provides a perovskite solar cell, which can be divided into a substrate 110, a transparent conductive layer 120, a hole transport layer 130, a light absorption layer 140, an electron transport layer 150, a hole blocking layer 160, and a back electrode layer 170 from bottom to top. The hole transport layer 130 is a single or stacked structure of nickel oxide prepared by radio frequency magnetron sputtering.

[0059] Nickel oxide is a chemically stable direct-bandgap semiconductor material with a wide bandgap and good light transmittance in the 400-800 nm wavelength range. As an inorganic material, nickel oxide has higher photothermal stability, which is more conducive to optimizing the stability of perovskite solar cells. Nickel oxide has a wide and tunable bandgap, and its energy levels closely match those of perovskites, making it suitable as a hole transport material in the commercialization of perovskite solar cells.

[0060] The perovskite solar cell provided in the above-mentioned embodiments of the present application uses radio frequency magnetron sputtering to deposit a single or stacked nickel oxide hole transport layer, which not only increases the carrier concentration of the nickel oxide hole transport layer, promotes carrier transport, but also improves the transmittance; the magnetron sputtering process not only improves the consistency and repeatability of the nickel oxide hole transport layer, but also facilitates large-area assembly line production.

[0061] The technical solution of the present application is described in detail below using this principle diagram in combination with specific embodiments.

[0062] Example 1

[0063] The steps for preparing the perovskite solar cell in Example 1 are as follows:

[0064] Step 1: Clean the substrate. Rinse the glass with deionized water. A cleaning agent is used for auxiliary cleaning during this process. The cleaning time is longer than 10 minutes. After cleaning, place the glass in an ultrasonic cleaner and then ultrasonically clean it with deionized water, acetone, and isopropyl alcohol for 30 minutes in sequence. After the ultrasonic cleaning is completed, transfer the substrate to a clean room and remove any residual liquid on the substrate surface with high-pressure pure nitrogen gas.

[0065] Step 2: Prepare a transparent conductive layer. Place a clean glass substrate into a magnetron sputtering chamber and evacuate it to the specified pressure. Then, use a 99.99% pure indium tin oxide target, fill it with an argon-oxygen mixture (Ar:O2=100:1), and sputter at 800W power, a sputtering temperature of 100°C, and a sputtering thickness of 90nm. This produces an ITO transparent conductive layer with a transmittance greater than 90% and a square resistance less than 20Ω / .

[0066] Step 3: Prepare the hole transport layer. The sample obtained in Step 2 was placed in a magnetron sputtering chamber and the vacuum was evacuated to the specified pressure. A 99.99% pure nickel oxide ceramic target was selected. The sputtering temperature was 100°C, the power was 800W, and the chamber was sputtered with an argon-oxygen mixture (Ar:O2 = 100:3) and then an argon-nitrogen mixture (Ar:O2 = 100:5). After sputtering, the sample was annealed in a muffle furnace at 300°C. This yielded a 20 nm thick oxygen-doped / nitrogen-doped nickel oxide layer with a transmittance exceeding 80%.

[0067] Step 4: Prepare a perovskite absorption layer. The sample obtained in step 3 was transferred to a glove box, and a 550 nm thick perovskite layer was prepared by solution method. The layer was annealed at 100°C for 30 min.

[0068] Step 5: Prepare the electron transport layer, hole blocking layer, and back electrode layer. Transfer the sample obtained in step 4 to a rotary evaporator, and sequentially evaporate 30 nm thick C60 as the electron transport layer, 8 nm thick BCP as the hole blocking layer, and 100 nm thick Ag as the electrode layer.

[0069] Please refer to FIG3 , which is a comparison diagram of the JV curves of the sputtered nickel oxide and the spin-coated nickel oxide-based perovskite solar cells prepared in this embodiment. As can be seen from FIG3 , the perovskite solar cell prepared in this embodiment has good cell performance.

[0070] Example 2

[0071] The perovskite solar cell prepared in Example 2 is prepared as follows: Step 1: Cleaning the substrate. First, rinse the stainless steel foil with deionized water. During this process, a cleaning agent is used for auxiliary cleaning. The cleaning time is longer than 10 minutes. After cleaning, the glass is placed in an ultrasonic cleaner and then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol for 30 minutes in sequence. After the ultrasonic cleaning is completed, the substrate is transferred to a dust-free shed and any residual liquid on the substrate surface is removed using high-pressure pure nitrogen gas.

[0072] Step 2: Prepare a transparent conductive layer. Place a clean glass substrate into a magnetron sputtering chamber and evacuate it to the specified pressure. Then, use an indium tin oxide target with a purity of 99.99%, fill it with an argon-oxygen mixture (Ar:O2=90:10), and sputter at a power of 800W. The sputtering temperature is 150°C, and the sputtering thickness is 150 nm. This produces an ITO transparent conductive layer with a transmittance greater than 90% and a square resistance less than 20 Ω / cm2.

[0073] Step 3: Prepare the hole transport layer. The sample obtained in Step 2 was placed in a magnetron sputtering chamber and the vacuum was evacuated to the specified pressure. A 99.99% pure nickel oxide ceramic target was selected. The sputtering temperature was 100°C, the power was 800W, and the chamber was filled with an argon-oxygen mixture (Ar:O2 = 95:5) and then an argon-nitrogen mixture (Ar:O2 = 80:20) for sputtering. After sputtering, the sample was annealed in a muffle furnace at 300°C. This yielded a 20 nm thick oxygen-doped / nitrogen-doped nickel oxide layer with a transmittance exceeding 80%.

[0074] Step 4: Prepare the perovskite absorption layer. Transfer the sample obtained in step 3 to a glove box, and prepare a 500 nm thick perovskite layer using a solution method. Anneal at 100°C for 30 min.

[0075] Step 5: Prepare the electron transport layer, hole blocking layer, and back electrode layer. Transfer the sample obtained in step 4 to a rotary evaporator, and sequentially evaporate 20 nm thick PCBM as the electron transport layer, 5 nm thick BCP as the hole blocking layer, and 150 nm thick Au as the electrode layer.

[0076] Example 3

[0077] The steps for preparing the perovskite solar cell in Example 3 are as follows:

[0078] Step 1: Clean the substrate. First, rinse the titanium foil with deionized water. During this process, use a detergent for auxiliary cleaning. The cleaning time is longer than 10 minutes. After cleaning, place the glass in an ultrasonic cleaner and then ultrasonically clean it with deionized water, acetone, and isopropyl alcohol for 30 minutes in sequence. After the ultrasonic cleaning is completed, transfer the substrate to a dust-free room and remove any residual liquid on the substrate surface with high-pressure pure nitrogen gas.

[0079] Step 2: Prepare a transparent conductive layer. Place a clean glass substrate into a magnetron sputtering chamber and evacuate it to a specified pressure. Then, use an indium tin oxide target with a purity of 99.99%, fill it with argon, and sputter at a power of 800W. The sputtering temperature is 20°C, and the sputtering thickness is 50 nm. This produces an ITO transparent conductive layer with a transmittance greater than 90% and a square resistance less than 20 Ω / cm2.

[0080] Step 3: Prepare the hole transport layer. Place the sample obtained in Step 2 into a magnetron sputtering chamber and evacuate it to the specified pressure. Then, use a 99.99% pure nickel oxide ceramic target. Sputter at a temperature of 100°C, a power of 800W, and argon gas. After sputtering, anneal the sample in a muffle furnace at 300°C. This yields a 20 nm thick, oxygen-doped / nitrogen-doped nickel oxide laminate with a transmittance exceeding 80%.

[0081] Step 4: Prepare the perovskite absorption layer. The sample obtained in step 3 was transferred to a glove box, and a 600 nm thick perovskite layer was prepared by solution method. The layer was annealed at 100°C for 30 min.

[0082] Step 5: Prepare the electron transport layer, hole blocking layer, and back electrode layer. Transfer the sample obtained in step 4 to a rotary evaporator, and sequentially evaporate 40 nm thick SnO2 as the electron transport layer, 5 nm thick BCP as the hole blocking layer, and 150 nm thick Cu as the electrode layer.

[0083] It can be understood that the various technical features of the above-described embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the various technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0084] The above are merely preferred embodiments of the present application and only specifically describe the technical principles of the present application. These descriptions are intended only to explain the principles of the present application and should not be construed in any way as limiting the scope of protection of the present application. Based on the explanations herein, any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present application, as well as other specific implementations of the present application that can be conceived by those skilled in the art without inventive effort, shall be included within the scope of protection of the present application.

Claims

1. A method for preparing a perovskite solar cell, characterized in that: The steps include: providing a substrate; Preparing a transparent conductive layer on the upper surface of the substrate; Depositing a hole transport layer on the transparent conductive layer by radio frequency magnetron sputtering, wherein the hole transport layer is nickel oxide of a single or laminated structure; Preparing a perovskite absorption layer on the upper surface of the hole transport layer; Preparing an electron transport layer on the upper surface of the perovskite absorption layer; Preparing a hole blocking layer on the upper surface of the electron transport layer; A back electrode layer is prepared on the upper surface of the hole blocking layer.

2. The method for preparing a perovskite solar cell according to claim 1, characterized in that: The step of providing a substrate specifically includes the following steps: The substrate was rinsed with deionized water, and after cleaning, the substrate was placed in an ultrasonic cleaner, and then ultrasonically cleaned with deionized water, acetone, and isopropanol for 30 minutes in sequence, and then the substrate was transferred to a dust-free shed, and the residual liquid on the surface of the substrate was removed with high-pressure pure nitrogen.

3. The method for preparing a perovskite solar cell according to claim 2, characterized in that: The substrate includes soda-lime glass, stainless steel foil, titanium foil, and PET.

4. The method for preparing a perovskite solar cell according to claim 1, characterized in that: The step of preparing a transparent conductive layer on the upper surface of the substrate specifically includes the following steps: placing the substrate into a magnetron sputtering chamber and evacuating the vacuum to a specified pressure, filling an argon-oxygen mixed gas for magnetron sputtering to obtain the transparent conductive layer, wherein the volume of O2 in the argon-oxygen mixed gas is 0≤O2≤10%, and the remainder is Ar, the sputtering temperature is 20~150°C, the sputtering thickness is 50~150 nm, the transmittance of the transparent conductive layer is greater than 90%, and the square resistance is less than 20Ω.

5. The method for preparing a perovskite solar cell according to claim 1, characterized in that: In the step of depositing a hole transport layer on the transparent conductive layer by using a radio frequency magnetron sputtering method, the following steps are specifically included: placing a sample with a transparent conductive layer prepared on the upper surface of the substrate into a magnetron sputtering chamber and evacuating the vacuum to a specified pressure, sequentially filling with argon oxygen mixed gas and argon nitrogen mixed gas for radio frequency magnetron sputtering, and annealing the sample after sputtering to obtain the hole transport layer, wherein: the sputtering temperature is 20~300°C, the sputtering thickness is 10~30 nm, the annealing temperature is 100~500°C, the thickness of the hole transport layer is 20nm, and the transmittance is higher than 80%.

6. The method for preparing a perovskite solar cell according to claim 5, characterized in that: In the RF magnetron sputtering, the target material is a nickel oxide ceramic target material of 590 mm*90 mm*5 mm and a purity of 99.99%, and the distance from the target material to the substrate is 80 mm; if the nickel oxide prepared by filling an argon-oxygen mixture is called A, and the nickel oxide prepared by filling an argon-nitrogen mixture is called B, then the prepared hole transport layer structure can be but is not limited to AA, BB, AABB, ABAB, BABA, BBAA, wherein the O2 content in the argon-oxygen mixture is 0≤O2≤5%, and the O2 content in the argon-nitrogen mixture is 0≤O2≤20%.

7. The method for preparing a perovskite solar cell according to claim 1, characterized in that: In the step of preparing a perovskite absorption layer on the upper surface of the hole transport layer, the following steps are specifically included: transferring the sample on which the hole transport layer is deposited on the transparent conductive layer to a glove box, preparing a perovskite layer with a thickness of 500-600 nm by a solution method, and annealing at 90-110 ° C for 25-40 min, wherein the perovskite absorption layer is a halide perovskite with a crystal structure of ABX3, wherein A is an organic cation or an inorganic cation, and B is a divalent metal ion Pb 2+ or Sn 2+ ; X is a halogen ion I, Br or Cl.

8. The method for preparing a perovskite solar cell according to claim 1, characterized in that: The step of preparing an electron transport layer on the upper surface of the perovskite absorption layer specifically includes the following steps: transferring the sample obtained by preparing the perovskite absorption layer on the upper surface of the hole transport layer to a rotary evaporator, and evaporating a 20-40 nm thick electron transport layer, wherein the electron transport layer can be one of C60, PCBM or SnO2.

9. The method for preparing a perovskite solar cell according to claim 1, characterized in that: The step of preparing a hole blocking layer on the upper surface of the electron transport layer specifically includes the following steps: transferring the sample on which the electron transport layer is prepared on the upper surface of the perovskite absorption layer to a rotary evaporator, and evaporating 5-10 nm thick BCP as a hole blocking layer.

10. The method for preparing a perovskite solar cell according to claim 1, characterized in that: The step of preparing a back electrode layer on the upper surface of the hole blocking layer specifically includes the following steps: transferring the sample on which the hole blocking layer is prepared on the upper surface of the electron transport layer to a rotary evaporator, and evaporating a 100-150 nm thick back electrode layer, wherein the back electrode layer may be but is not limited to Au, Ag, Cu, or Al.

11. A perovskite solar cell, characterized in that: The perovskite solar cell can be divided into a substrate, a transparent conductive layer, a hole transport layer, a light absorption layer, an electron transport layer, a hole blocking layer, and a back electrode layer from bottom to top. The hole transport layer is a single or laminated nickel oxide prepared by radio frequency magnetron sputtering.

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