Perovskite solar cell with all film layers prepared based on controllable magnetron sputtering method

Abstract

The invention discloses a perovskite solar cell with all film layers prepared based on a controllable magnetron sputtering method. A perovskite solar cell with all film layers prepared based on a controllable magnetron sputtering method comprises a transparent conductive layer, an electron transport layer, a perovskite photoactive layer, a hole transport layer and a top electrode layer, and the transparent conductive layer, the electron transport layer, the perovskite photoactive layer, the hole transport layer and the top electrode layer are prepared by adopting the magnetron sputtering method. All the film layers of the perovskite solar cell provided by the invention are prepared by the magnetron sputtering method, so that other equipment is prevented from being added, and controllable preparation of all the film layers of the perovskite solar cell by the magnetron sputtering method is realized.

Description

Technical Field

[0001] The present invention relates to the field of solar cell power generation, and particularly to a perovskite solar cell prepared by a controllable magnetron sputtering method for all film layers. Background Art

[0002] At present, the perovskite solar cell industry is in an important stage from laboratory to industrialization, and both wet process and dry process, as two important routes for the industrialization of perovskite solar cells, are being continuously promoted. The wet process has the advantages of high raw material utilization rate, low cost, fast production rate, etc., but the control of film thickness and the uniformity of film layers need to be further improved; the dry process has the advantages of better control of large-area thickness and uniformity and low requirement for the flatness of the substrate, but its cost is relatively high. In the dry process, magnetron sputtering, as a mature thin film preparation technology, has great application potential in the preparation of perovskite cells. Similar to the vacuum evaporation technology, magnetron sputtering also appears in multiple links such as the hole transport layer, electron transport layer, and back electrode of perovskite solar cells. Professor Zou Dechun of Peking University proposed that high-quality perovskite thin films were prepared by magnetron sputtering, realizing controllable composition, solvent-free, large-area and batch production. This makes it possible to prepare perovskite solar cells entirely by magnetron sputtering method. However, perovskite solar cells contain different materials such as metals, oxides, and organic-inorganic hybrids. How to achieve the controllable preparation of all film layers of perovskite solar cells is one of the difficulties in the preparation of perovskite solar cells by magnetron sputtering method. Summary of the Invention

[0003] The object of the present invention is to provide a perovskite solar cell prepared by a controllable magnetron sputtering method for all film layers. All film layers of the perovskite solar cell proposed by the present invention are prepared by magnetron sputtering method, avoiding the addition of other equipment and realizing the controllable preparation of all film layers of perovskite solar cells by magnetron sputtering method.

[0004] The present invention is realized by the following technical solutions:

[0005] A perovskite solar cell prepared by a controllable magnetron sputtering method for all film layers includes a transparent conductive layer, an electron transport layer, a perovskite photoactive layer, a hole transport layer, and a top electrode layer; when the magnetron sputtering method uses a planar target to prepare the transparent conductive layer or the top electrode layer, the surface magnetic field strength is 0.025 - 0.05T, and the target material is a planar target; when the magnetron sputtering method prepares the perovskite photoactive layer, a weakening sheet is arranged outside the planar target magnet to reduce the surface magnetic field strength to 0.01 - 0.02T; when the magnetron sputtering method prepares the electron transport layer and the hole transport layer, a strengthening sheet is arranged outside the planar target to increase the surface magnetic field strength to 0.055 - 0.120T.

[0006] Preferably, the material of the attenuation sheet is selected from pure iron, low-carbon steel, iron-silicon alloy, iron-aluminum alloy, iron-silicon-aluminum alloy, nickel-iron alloy, iron-cobalt alloy, and soft magnetic ferrite; the material of the reinforcement sheet is selected from at least one of neodymium iron boron, samarium cobalt, ferrite, alnico, and iron chromium cobalt. The perovskite photoactive layer prepared by the magnetron sputtering method can obtain the required perovskite photoactive layer without any post-treatment.

[0007] Preferably, the perovskite solar cell is a normal-structure perovskite solar cell or a reverse-structure perovskite solar cell. The normal-structure perovskite solar cell sequentially includes a transparent conductive layer / hole transport layer / perovskite photoactive layer / electron transport layer / top electrode layer, and the reverse-structure perovskite solar cell sequentially includes a transparent conductive layer / electron transport layer / perovskite photoactive layer / hole transport layer / top electrode layer.

[0008] More preferably, the structure of the perovskite photoactive layer is ABX3, where A is selected from one or more of Cs, MA, and FA, B is selected from one or more of Pb, Sn, Ge, Bi, In, and Sb, and X is selected from one or more of I, Br, and Cl.

[0009] More preferably, the transparent conductive layer is oxide ITO, FTO, or AZO; the top electrode layer is a metal electrode or a dielectric layer / metal layer / dielectric layer, and the metal electrode is selected from one or more of Ag, Au, and Al.

[0010] More preferably, the electron transport layer is selected from one or more of SnO2, TiO2, ZnO, ZnS, SrSnO3, NiO, and Nb2O5, and the hole transport layer is selected from one or more of NiO, CuSCN, CuI, Cu2O, V2O5, WO3, CuS, MoO3, Co3O4, NiCo2O4, SrCO3, CuCrO2, CuScO2, CuGaO2, and graphene oxide.

[0011] More preferably, an interface modification layer is added between the perovskite photoactive layer and the electron transport layer and / or between the perovskite photoactive layer and the hole transport layer. The interface modification layer is selected from one or more of WO3, NiO, V2O5, MoO3, MoS2, TiO2, ZnO, LiF, Cs2CO3, CdS, SnO2, and graphene oxide; a blocking buffer layer is added between the hole transport layer and the top electrode layer and / or between the electron transport layer and the top electrode layer. The blocking buffer layer is selected from one or more of MoO3, Fe3O4, V2O5, Cu2O, NiO, and ZnO.

[0012] Further preferably, the thickness of the transparent conductive layer is 10 - 2000 nm, the thickness of the electron transport layer is 10 - 200 nm, the thickness of the perovskite photoactive layer is 300 - 800 nm, the thickness of the hole transport layer is 10 - 200 nm, and the thickness of the top electrode layer is 20 - 500 nm.

[0013] The present invention also protects a preparation method of the perovskite solar cell with all film layers prepared by the controllable magnetron sputtering method. The perovskite solar cell is a normal structure perovskite solar cell or a reverse structure. The preparation method of the normal structure perovskite solar cell includes the following steps: (1) Using a planar target made of a conductive oxide, sputter the transparent conductive layer on the substrate by magnetron sputtering. Use DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (2) Add a reinforcing sheet outside the planar target magnet, and use a planar target made of a hole transport layer material to magnetron sputter the hole transport layer on the transparent conductive layer. Use DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (3) Add a weakening sheet outside the planar target magnet, and use an α-phase perovskite planar target made of a perovskite material to sputter the perovskite photoactive layer on the hole transport layer. Use RF sputtering, the substrate temperature is 25°C - 300°C, the sputtering power is 2 - 100 W, the atmosphere is a hydrogen-argon mixture, hydrogen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 1 - 600 minutes; without any subsequent treatment, an α-phase perovskite photoactive layer can be obtained; (4) Add a reinforcing sheet outside the planar target magnet, and use a planar target made of an electron transport layer material to magnetron sputter the electron transport layer on the perovskite photoactive layer. Use DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (5) Prepare the top electrode layer by magnetron sputtering method. Use DC sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 500 W, the atmosphere is pure argon, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; thus, the normal structure perovskite solar cell is obtained. Room temperature is also called normal temperature or general temperature, and is generally defined as 25°C.

[0014] Preferably, the method for preparing the inverted perovskite solar cell includes the following steps: (1) Using magnetron sputtering, a transparent conductive layer is sputtered on a substrate with a planar target made of a conductive oxide. DC or RF sputtering is used, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is a mixed gas of oxygen and argon, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (2) A reinforcing sheet is added to the outer layer of the planar target magnet, and a planar target made of an electron transport layer material is used to magnetron sputter an electron transport layer on the transparent conductive layer. DC or RF sputtering is used, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is a mixed gas of oxygen and argon, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (3) A weakening sheet is added to the outer layer of the planar target magnet, and an α-phase perovskite planar target made of a perovskite material is used to sputter a perovskite photoactive layer on the electron transport layer. RF sputtering is used, the substrate temperature is 25°C - 300°C, the sputtering power is 2 - 100 W, the atmosphere is a mixed gas of hydrogen and argon, hydrogen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 1 - 600 minutes; without any subsequent treatment, an α-phase perovskite photoactive layer can be obtained; (4) A reinforcing sheet is added to the outer layer of the planar target magnet, and a planar target made of a hole transport layer material is used to magnetron sputter a hole transport layer on the perovskite photoactive layer. DC or RF sputtering is used, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is a mixed gas of oxygen and argon, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (5) A top electrode layer is prepared by magnetron sputtering. DC sputtering is used, the substrate temperature is room temperature, the sputtering power is 20 - 500 W, the atmosphere is pure argon, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; thus, the inverted perovskite solar cell is obtained. The oxygen:argon = 0 - 20% proposed in the present invention refers to the volume ratio of oxygen to argon.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0016] 1. The present invention uses a reinforcing sheet and a weakening sheet to regulate the magnetic field on the surface of the planar target, broadening the range of sputterable materials and achieving controllable sputtering of different materials;

[0017] 2. The present invention regulates the magnetic field on the surface of the planar target to achieve controllable sputtering of different materials. Through process adjustment, the damage to the bottom film layer caused by magnetron sputtering is reduced;

[0018] 3. All film layers of the present invention are prepared by magnetron sputtering, avoiding the addition of other equipment and achieving efficient utilization of the equipment. Description of the Drawings

[0019] Figure 1 Structural schematic diagram of a magnetic field and a planar target used in the present invention;

[0020] Figure 2 Structural schematic diagram of a magnetic field and a planar target with a reinforcing sheet in the present invention;

[0021] Figure 3 Structural schematic diagram of a magnetic field and a planar target with a weakening sheet in the present invention;

[0022] Figure 4 Structural schematic diagram of a perovskite solar cell with a formal structure in Embodiment 1 of the present invention;

[0023] Figure 5 Structural schematic diagram of a perovskite solar cell with an inverted structure in Embodiment 2 of the present invention;

[0024] Figure 6 Structural schematic diagram of a perovskite solar cell with a formal structure having an interface modification layer added between a perovskite photoactive layer and a hole transport layer in Embodiment 3 of the present invention;

[0025] Figure 7 Structural schematic diagram of a perovskite solar cell with a formal structure having a barrier buffer layer added between a hole transport layer and a top electrode layer in Embodiment 4 of the present invention;

[0026] Figure 8 XRD diagrams of the α-phase perovskite target, the perovskite target after sputtering without adding a weakening sheet, and the perovskite target after sputtering with a weakening sheet prepared in Embodiment 1 of the present invention;

[0027] Explanation of reference numerals: 1, magnet; 2, planar target; 3, reinforcing sheet; 4, weakening sheet; 5, glass substrate; 6, transparent conductive layer; 7, hole transport layer; 8, perovskite photoactive layer; 9, electron transport layer; 10, top electrode layer; 11, interface modification layer; 12, barrier buffer layer; 13, dielectric layer; 14, metal layer. Detailed implementation manners

[0028] The present invention will be further described in detail below in conjunction with embodiments. These embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. For the experimental methods without specific conditions in the following embodiments, they are generally carried out according to the conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are regarded as raw materials and reagents that can be obtained through conventional commercial channels such as the market.

[0029] A perovskite solar cell prepared by a controllable magnetron sputtering method for all film layers, comprising a transparent conductive layer 6, an electron transport layer 9, a perovskite photoactive layer 8, a hole transport layer 7, and a top electrode layer 10. The transparent conductive layer 6, the electron transport layer 9, the perovskite photoactive layer 8, the hole transport layer 7, and the top electrode layer 10 are all prepared by magnetron sputtering. The perovskite photoactive layer prepared by the magnetron sputtering method can obtain the required perovskite photoactive layer without any post-treatment.

[0030] The perovskite solar cell is a normal structure perovskite solar cell or an inverted structure perovskite solar cell. The normal structure perovskite solar cell sequentially includes a transparent conductive layer / hole transport layer / perovskite photoactive layer / electron transport layer / top electrode layer. The inverted structure perovskite solar cell sequentially includes a transparent conductive layer / electron transport layer / perovskite photoactive layer / hole transport layer / top electrode layer.

[0031] A magnet 1 is installed below the planar target 2 used in the magnetron sputtering method, with the central and peripheral parts being N and S poles respectively. When using the planar target to prepare the transparent conductive layer 6 or the top electrode layer 10 by the magnetron sputtering method, the surface magnetic field magnitude is 0.025 - 0.05 T, and the target material is a planar target. When preparing the perovskite photoactive layer 8 by the magnetron sputtering method, a weakening sheet 4 is set outside the planar target magnet to reduce the surface magnetic field magnitude to 0.01 - 0.02 T. The material of the weakening sheet is selected from pure iron, low-carbon steel, iron-silicon alloys, iron-aluminum alloys, iron-silicon-aluminum alloys, nickel-iron alloys, iron-cobalt alloys, and soft magnetic ferrites. When preparing the electron transport layer 9 and the hole transport layer 7 by the magnetron sputtering method, a strengthening sheet 3 is set outside the planar target to increase the surface magnetic field magnitude to 0.055 - 0.120 T. The material of the strengthening sheet is selected from at least one of neodymium iron boron, samarium cobalt, ferrite, alnico, and iron chromium cobalt.

[0032] In the following embodiments, the preferred substrate is a glass substrate 5.

[0033] The structure of the perovskite photoactive layer 8 is ABX3, where A is selected from one or more of Cs, MA, and FA, B is selected from one or more of Pb, Sn, Ge, Bi, In, and Sb, and X is selected from one or more of I, Br, and Cl. In the following embodiments, preferably, the structure of the perovskite photoactive layer includes FAPbI3, CsPbI3, MA 0.2 FA 0.8 PbI3, MA 0.1 Cs 0.9 PbI 2.8 Br 0.2 etc.

[0034] The transparent conductive layer 6 is oxide ITO, FTO, or AZO; the top electrode layer 10 is a metal electrode or a dielectric layer 13 / metal layer 14 / dielectric layer 13, and the metal electrode is selected from Ag, Au, and Al.

[0035] The electron transport layer 9 is selected from one or more of SnO2, TiO2, ZnO, ZnS, SrSnO3, NiO, and Nb2O5, and the hole transport layer 7 is selected from one or more of NiO, CuSCN, CuI, Cu2O, V2O5, WO3, CuS, MoO3, Co3O4, NiCo2O4, SrCO3, CuCrO2, CuScO2, CuGaO2, and graphene oxide.

[0036] An interface modification layer 11 is added between the perovskite photoactive layer 8 and the electron transport layer 9 and / or between the perovskite photoactive layer 8 and the hole transport layer 7. The interface modification layer 11 is selected from one or more of WO3, NiO, V2O5, MoO3, MoS2, TiO2, ZnO, LiF, Cs2CO3, CdS, SnO2, and graphene oxide.

[0037] A blocking buffer layer 12 is added between the hole transport layer 7 and the top electrode layer 10 and / or between the electron transport layer 9 and the top electrode layer 10. The blocking buffer layer 12 is selected from one or more of MoO3, Fe3O4, V2O5, Cu2O, NiO, and ZnO.

[0038] When the interface modification layer 11 is prepared by magnetron sputtering using a planar target, a weakening sheet 4 is provided outside the planar target magnet to reduce the surface magnetic field magnitude to 0.01 - 0.02 T. When the blocking buffer layer 12 is prepared by magnetron sputtering using a planar target, a strengthening sheet 3 is provided outside the planar target to increase the surface magnetic field magnitude to 0.055 - 0.120 T.

[0039] The thickness of the transparent conductive layer is 10 - 2000 nm, the thickness of the electron transport layer is 10 - 200 nm, the thickness of the perovskite photoactive layer is 300 - 800 nm, the thickness of the hole transport layer is 10 - 200 nm, and the thickness of the top electrode layer is 20 - 500 nm.

[0040] A method for preparing a formal structure perovskite solar cell, comprising the following steps: (1) cleaning and drying a substrate 5, and performing ultraviolet ozone treatment or plasma treatment; (2) using a planar target made of a conductive oxide to sputter a transparent conductive layer 6 on the substrate 5 by magnetron sputtering, using DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (3) adding a reinforcing sheet 3 to the outer layer of the planar target magnet, using a planar target made of a hole transport layer material, and magnetron sputtering a hole transport layer 7 on the transparent conductive layer 6, using DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (4) adding a weakening sheet 4 to the outer layer of the planar target magnet, using an α-phase perovskite planar target made of a perovskite material, and sputtering a perovskite photoactive layer 8 on the hole transport layer, using RF sputtering, the substrate temperature is 25°C-300°C, the sputtering power is 2-100W, the atmosphere is a hydrogen-argon mixture, hydrogen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 1-600 minutes; without any subsequent treatment, an α-phase perovskite photoactive layer can be obtained; (5) adding a reinforcing sheet 3 to the outer layer of the planar target magnet, using a planar target made of an electron transport layer material, and magnetron sputtering an electron transport layer 9 on the perovskite photoactive layer 8, using DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (6) preparing a top electrode layer 10 by magnetron sputtering method, using DC sputtering, the substrate temperature is room temperature, the sputtering power is 20-500W, the atmosphere is pure argon, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; thus, a formal structure perovskite solar cell is obtained.

[0041] The preparation method of the inverted perovskite solar cell is as follows: (1) Clean and dry the substrate 3, and perform ultraviolet ozone treatment or plasma treatment; (2) Use a planar target made of a conductive oxide to sputter a transparent conductive layer 6 on the substrate 3 by magnetron sputtering. Use DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (3) Add a reinforcing sheet 3 to the outer layer of the planar target magnet, and use a planar target made of an electron transport layer material to magnetron sputter an electron transport layer 9 on the transparent conductive layer. Use DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (4) Add a weakening sheet 4 to the outer layer of the planar target magnet, and use an α-phase perovskite planar target made of a perovskite material to sputter a perovskite photoactive layer 8 on the electron transport layer. Use RF sputtering, the substrate temperature is 25°C - 300°C, the sputtering power is 2 - 100 W, the atmosphere is a hydrogen-argon mixture, hydrogen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 1 - 600 minutes; No post-treatment is required to obtain an α-phase perovskite photoactive layer; (5) Add a reinforcing sheet to the outer layer of the planar target magnet, and use a planar target made of a hole transport layer material to magnetron sputter a hole transport layer 7 on the perovskite photoactive layer 8. Use DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 200 W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0 - 20%, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; (6) Use the magnetron sputtering method to prepare a top electrode layer 10. Use DC sputtering, the substrate temperature is room temperature, the sputtering power is 20 - 500 W, the atmosphere is pure argon, the sputtering pressure is 0.06 - 6 Pa, and the sputtering time is 5 - 480 minutes; Then the inverted perovskite solar cell is obtained.

[0042] Preferably, in the following embodiments, the transparent conductive layer 6 is prepared by DC or RF sputtering. The substrate temperature is room temperature, the sputtering power is 60 - 80 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.06 - 0.2 Pa, and the sputtering time is 30 - 50 minutes; the hole transport layer 7 is prepared by RF sputtering. The substrate temperature is room temperature, the sputtering power is 60 - 100 W, the atmosphere is oxygen-argon atmosphere, oxygen:argon = 0 - 5%, the sputtering pressure is 0.06 - 0.1 Pa, and the sputtering time is 30 minutes; the perovskite photoactive layer 8 is prepared by RF sputtering. The substrate temperature is 100 °C - 160 °C, the sputtering power is 20 - 25 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.2 Pa, and the sputtering time is 120 - 150 minutes; the electron transport layer 9 is prepared by RF sputtering. The substrate temperature is room temperature, the sputtering power is 80 - 100 W, the atmosphere is oxygen-argon atmosphere, oxygen:argon = 0 - 5%, the sputtering pressure is 0.06 - 0.1 Pa, and the sputtering time is 30 minutes; (6) The top electrode layer 10 is prepared by magnetron sputtering method. DC sputtering is used, the substrate temperature is room temperature, the sputtering power is 30 - 100 W, the atmosphere is pure argon, the sputtering pressure is 0.2 Pa, and the sputtering time is 20 - 60 minutes.

[0043] Example 1

[0044] Reference Figure 1-4 , A preparation method of a formal structure perovskite solar cell with all film layers prepared by a controllable magnetron sputtering method, comprising the following steps: (1) Clean the glass substrate 5 ultrasonically with ethanol, isopropanol, and deionized water in sequence, dry it with nitrogen, and perform ultraviolet ozone treatment for 20 minutes; (2) Using the magnetron sputtering method, with the structure of the magnetic field and planar target as shown in Figure 1 , on the glass substrate 5, a planar target made of conductive oxide ITO is used to magnetron sputter the transparent conductive layer 6. DC sputtering is used, the substrate temperature is room temperature, the sputtering power is 60 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.2 Pa, the sputtering time is 30 minutes, and the thickness of the transparent conductive layer 6 is 100 nm; (3) Add a neodymium iron boron reinforcement sheet to the outer layer of the planar target magnet to make the surface magnetic field size 0.055 - 0.120 T, as shown in Figure 2 , using a planar target made of hole transport layer material NiO, magnetron sputter the hole transport layer 7 on the transparent conductive layer 6. RF sputtering is used, the substrate temperature is room temperature, the sputtering power is 60 W, the atmosphere is oxygen-argon atmosphere, oxygen:argon = 5%, the sputtering pressure is 0.1 Pa, the sputtering time is 30 minutes, and the thickness of the hole transport layer 7 is 30 nm; (4) Add an iron-aluminum alloy weakening sheet 4 to the outer layer of the planar target magnet to make the surface magnetic field size 0.01 - 0.02 T, as shown in Figure 3As shown in the figure, a planar target of α-phase perovskite material made of perovskite material FAPbI3 is used. The perovskite photoactive layer 8 is sputtered on the hole transport layer 7. Radio frequency sputtering is adopted, the substrate temperature is 130 °C, the sputtering power is 20 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.2 Pa, and the sputtering time is 120 minutes; without any post-treatment, an α-phase perovskite photoactive layer can be obtained, and the thickness of the perovskite photoactive layer 8 is 500 nm; (5) A neodymium iron boron reinforcing sheet 3 is added to the outer layer of the planar target magnet to make the surface magnetic field size 0.055 - 0.120 T, as Figure 2 As shown in the figure, a planar target made of electron transport layer material ZnO is used. The electron transport layer 9 is magnetron sputtered on the perovskite photoactive layer 8. Radio frequency sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 100 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.06 Pa, and the sputtering time is 30 minutes. The thickness of the electron transport layer 9 is 30 nm; (6) Using Figure 1 As shown in the magnetic field and planar target structure, using an Ag target, the top electrode layer 10 is prepared. DC sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 200 W, the atmosphere is pure argon, the sputtering pressure is 0.2 Pa, and the sputtering time is 20 minutes. The thickness of the top electrode layer is 100 nm; that is, the formal structure perovskite solar cell is obtained.

[0045] In order to compare the effects of adding or not adding a weakening sheet in magnetron sputtering, XRD tests were carried out on the perovskite target. Figure 8 The XRD patterns of the fabricated α-phase perovskite target, the perovskite target after sputtering without adding a weakening sheet, and the perovskite target after sputtering with adding a weakening sheet are shown. It can be seen that the original perovskite target is a pure α-phase; after magnetron sputtering without adding a weakening sheet, the PbI2 phase appears in the target, indicating that PbI2 precipitates on the surface of the target; after magnetron sputtering with adding a weakening sheet, the target is still a pure α-phase, indicating that the target is not affected.

[0046] Example 2

[0047] Refer to Figure 1-3 and Figure 5 A preparation method of a planar structure perovskite solar cell based on a controllable magnetron sputtering method for preparing all film layers includes the following steps: (1) The glass substrate 5 is ultrasonically cleaned successively with ethanol, isopropanol, and deionized water, and dried with nitrogen, and plasma treatment is carried out for 20 minutes; (2) Using magnetron sputtering method, using as Figure 1The structure of the magnetic field and the planar target is as follows. A planar target made of conductive oxide FTO is formed on a glass substrate 5. A transparent conductive layer 6 is magnetron sputtered. DC sputtering is used, the substrate temperature is room temperature, the sputtering power is 80 W, the atmosphere is pure argon, the sputtering pressure is 0.06 Pa, the sputtering time is 50 minutes, and the thickness of the transparent conductive layer 6 is 100 nm; (3) A reinforcing sheet 3 is added to the outer layer of the planar target magnet to make the surface magnetic field strength 0.055 - 0.120 T, as shown in Figure 2 shown. A planar target made of electron transport layer material TiO2 is used. An electron transport layer 9 is magnetron sputtered on the transparent conductive layer 6. RF sputtering is used, the substrate temperature is room temperature, the sputtering power is 80 W, the atmosphere is an oxygen-argon atmosphere, oxygen:argon = 5%, the sputtering pressure is 0.1 Pa, the sputtering time is 30 minutes, and the thickness of the electron transport layer 9 is 50 nm; (4) A weakening sheet 4 is added to the outer layer of the planar target magnet to make the surface magnetic field strength 0.01 - 0.02 T, as shown in Figure 3 shown. A planar target of α-phase perovskite material made of perovskite material CsPbI3 is used. A perovskite photoactive layer 8 is sputtered on the electron transport layer 9. RF sputtering is used, the substrate temperature is 160 °C, the sputtering power is 25 W, the atmosphere is pure argon, the sputtering pressure is 0.2 Pa, the sputtering time is 150 minutes; The α-phase perovskite photoactive layer can be obtained without any post-treatment, and the thickness of the perovskite photoactive layer 8 is 400 nm; (5) A reinforcing sheet 3 is added to the outer layer of the planar target magnet to make the surface magnetic field strength 0.055 - 0.120 T, as shown in Figure 2 shown. A planar target made of hole transport layer material WO3 is used. A hole transport layer 7 is magnetron sputtered on the perovskite photoactive layer 8. RF sputtering is used, the substrate temperature is room temperature, the sputtering power is 100 W, the atmosphere is pure argon, the sputtering pressure is 0.06 Pa, the sputtering time is 30 minutes, and the thickness of the hole transport layer 7 is 50 nm; (6) Using the Figure 1 shown magnetic field and planar target structure, using an Au target, a top electrode layer 10 is prepared. DC sputtering is used, the substrate temperature is room temperature, the sputtering power is 200 W, the atmosphere is pure argon, the sputtering pressure is 0.2 Pa, the sputtering time is 20 minutes, and the thickness of the top electrode layer is 70 nm; That is, a reverse-structure perovskite solar cell is obtained.

[0048] Example 3

[0049] Reference Figure 1-3 and Figure 6 , A method for preparing a normal-structure perovskite solar cell with an interface modification layer added between the perovskite and the transport layer, including the following steps: (1) The glass substrate 5 is ultrasonically cleaned in sequence with ethanol, isopropanol, and deionized water, dried with nitrogen, and subjected to ultraviolet ozone treatment for 20 minutes; (2) Using the magnetron sputtering method, using as shown in Figure 1The structure of the magnetic field and planar target is as follows. A planar target made of conductive oxide AZO is used on a glass substrate 5. A transparent conductive layer 6 is magnetron sputtered. DC sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 60 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.2 Pa, the sputtering time is 30 minutes, and the thickness of the transparent conductive layer 6 is 100 nm; (3) A reinforcing sheet 3 is added to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.055 - 0.120 T, as shown in Figure 2 shown. A planar target made of hole transport layer material NiO is used. A hole transport layer 7 is magnetron sputtered on the transparent conductive layer 6. RF sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 60 W, the atmosphere is oxygen-argon atmosphere, oxygen:argon = 5%, the sputtering pressure is 0.1 Pa, the sputtering time is 30 minutes, and the thickness of the hole transport layer is 30 nm; (4) A weakening sheet 4 is added to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.01 - 0.02 T, as shown in Figure 3 shown. A planar target made of perovskite material MA 0.2 FA 0.8 PbI3 is used. A perovskite photoactive layer 8 is sputtered on the hole transport layer 7. RF sputtering is adopted, the substrate temperature is 100 °C, the sputtering power is 20 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.2 Pa, the sputtering time is 120 minutes; An α-phase perovskite photoactive layer can be obtained without any post-treatment, and the thickness of the perovskite photoactive layer 8 is 500 nm; (5) A weakening sheet 4 is added to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.01 - 0.02 T, as shown in Figure 3 shown. A planar target made of MoS2 is used on the perovskite photoactive layer 8. An interface modification layer 11 is prepared by magnetron sputtering. RF sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 60 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.1 Pa, the sputtering time is 30 minutes, and the thickness of the interface modification layer is 10 nm; (6) A reinforcing sheet 3 is added to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.055 - 0.120 T, as shown in Figure 2 shown. A planar target made of electron transport layer material SnO2 is used. An electron transport layer 9 is magnetron sputtered on the interface modification layer 11. RF sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 100 W, the atmosphere is pure argon atmosphere, the sputtering pressure is 0.06 Pa, the sputtering time is 30 minutes, and the thickness of the electron transport layer is 30 nm; (6) Using the magnetic field and planar target structure shown in Figure 1 shown, using an Ag target, a top electrode layer 10 is prepared. DC sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 100 W, the atmosphere is pure argon, the sputtering pressure is 0.2 Pa, the sputtering time is 40 minutes, and the thickness of the top electrode layer is 100 nm; That is, a formal structure perovskite solar cell with an interface modification layer is obtained.

[0050] Example 4

[0051] Reference Figure 1-3 and Figure 7 , a method for preparing a perovskite solar cell with a reverse structure having a barrier buffer layer between a transport layer and a top electrode layer, comprising the following steps: (1) ultrasonically cleaning a glass substrate 5 successively with ethanol, isopropyl alcohol, and deionized water, drying it with nitrogen, and performing ultraviolet ozone treatment for 20 minutes; (2) using a magnetron sputtering method, with the structure of a magnetic field and a planar target as shown in Figure 1 , using a planar target made of a conductive oxide FTO on the glass substrate 5, magnetron sputtering a transparent conductive layer 6, using DC sputtering, with the substrate temperature at room temperature, the sputtering power at 80 W, the atmosphere being a pure argon atmosphere, the sputtering pressure at 0.06 Pa, the sputtering time at 50 minutes, and the thickness of the transparent conductive layer 6 being 100 nm; (3) adding a reinforcing sheet to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.055 - 0.120 T, as shown in Figure 2 , using a planar target made of an electron transport layer material SnO2, magnetron sputtering an electron transport layer 9 on the transparent conductive layer 6, using RF sputtering, with the substrate temperature at room temperature, the sputtering power at 80 W, the atmosphere being an oxygen-argon atmosphere, oxygen:argon = 5%, the sputtering pressure at 0.1 Pa, the sputtering time at 30 minutes, and the thickness of the electron transport layer 9 being 50 nm; (4) adding a weakening sheet 4 to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.01 - 0.02 T, as shown in Figure 3 , using a planar target made of a perovskite material MA 0.1 Cs 0.9 PbI 2.8 Br 0.2 to make a planar target of an α-phase perovskite material, sputtering a perovskite photoactive layer 8 on the electron transport layer 9, using RF sputtering, with the substrate temperature at 160 °C, the sputtering power at 25 W, the atmosphere being a pure argon atmosphere, the sputtering pressure at 0.2 Pa, the sputtering time at 150 minutes; an α-phase perovskite photoactive layer can be obtained without any subsequent treatment, and the thickness of the perovskite photoactive layer 8 is 400 nm; (5) adding a reinforcing sheet 3 to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.055 - 0.120 T, as shown in Figure 2 , using a planar target made of a hole transport layer material Cu2O, magnetron sputtering a hole transport layer 7 on the perovskite photoactive layer 8, using RF sputtering, with the substrate temperature at room temperature, the sputtering power at 100 W, the atmosphere being a pure argon atmosphere, the sputtering pressure at 0.06 Pa, the sputtering time at 30 minutes, and the thickness of the hole transport layer 7 being 50 nm; (6) adding a reinforcing sheet 3 to the outer layer of the planar target magnet to make the surface magnetic field magnitude 0.055 - 0.120 T, as shown in Figure 2As shown in the figure, a planar target made of MoO3 is used to magnetron sputter a blocking buffer layer 12 on the hole transport layer 7. Radio frequency sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 50 W, the atmosphere is a pure argon atmosphere, the sputtering pressure is 0.06 Pa, the sputtering time is 10 minutes, and the thickness of the blocking buffer layer 12 is 10 nm; (7) Using Figure 1 the magnetic field and planar target structure shown in the figure, an ITO target is used to magnetron sputter a dielectric layer 13. DC sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 60 W, the atmosphere is a pure argon atmosphere, the sputtering pressure is 0.2 Pa, and the sputtering time is 20 minutes; An Ag target is used to magnetron sputter an ultra-thin metal layer 14. DC sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 30 W, the atmosphere is pure argon, the sputtering pressure is 0.2 Pa, and the sputtering time is 20 minutes; An ITO target is used to magnetron sputter a dielectric layer 13. DC sputtering is adopted, the substrate temperature is room temperature, the sputtering power is 60 W, the atmosphere is a pure argon atmosphere, the sputtering pressure is 0.2 Pa, and the sputtering time is 20 minutes; that is, the top electrode layer with a dielectric layer / metal layer / dielectric layer structure, and the thickness of the top electrode layer is 100 nm; that is, a perovskite solar cell with a blocking buffer layer is obtained.

[0052] The description of the above embodiments is only used to help understand the technical solution and its core idea of the present invention. It should be noted that for those skilled in the art of this technology, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A perovskite solar cell with all film layers prepared by a controllable magnetron sputtering method, characterized in that: It comprises a transparent conductive layer, an electron transport layer, a perovskite photoactive layer, a hole transport layer and a top electrode layer; when the magnetron sputtering method uses a planar target to prepare the transparent conductive layer or the top electrode layer, the surface magnetic field is 0.025-0.05T, and the target material is a planar target; when the magnetron sputtering method is used to prepare the perovskite photoactive layer, a weakening sheet is arranged on the outer layer of the planar target magnet to reduce the surface magnetic field to 0.01-0.02T; when the magnetron sputtering method is used to prepare the electron transport layer and the hole transport layer, a reinforcing sheet is arranged on the outer layer of the planar target to increase the surface magnetic field to 0.055-0.120T.

2. The perovskite solar cell according to claim 1, characterized in that The material of the weakening sheet is selected from pure iron, low carbon steel, iron-silicon alloy, iron-aluminum alloy, iron-silicon-aluminum alloy, nickel-iron alloy, iron-cobalt alloy and soft magnetic ferrite; the material of the strengthening sheet is selected from at least one of neodymium iron boron, samarium cobalt, ferrite, aluminum nickel cobalt and iron chromium cobalt.

3. The perovskite solar cell according to claim 1 or 2, characterized in that: The perovskite solar cell is a regular structure perovskite solar cell or a reverse structure perovskite solar cell. The regular structure perovskite solar cell includes a transparent conductive layer / hole transport layer / perovskite photoactive layer / electron transport layer / top electrode layer in sequence, and the reverse structure perovskite solar cell includes a transparent conductive layer / electron transport layer / perovskite photoactive layer / hole transport layer / top electrode layer in sequence.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that: The structure of the perovskite photoactive layer is ABX3, the A position is selected from one or more of Cs, MA and FA, the B position is selected from one or more of Pb, Sn, Ge, Bi, In and Sb, and X is selected from one or more of I, Br and Cl.

5. The perovskite solar cell according to any one of claims 1 to 3, characterized in that: The transparent conductive layer is oxide ITO, FTO or AZO; the top electrode layer is a metal electrode or a dielectric layer / metal layer / dielectric layer, and the metal electrode is selected from one or more of Ag, Au and Al.

6. The perovskite solar cell according to any one of claims 1 to 3, characterized in that: The electron transport layer is selected from one or more of SnO2, TiO2, ZnO, ZnS, SrSnO3, NiO and Nb2O5, and the hole transport layer is selected from one or more of NiO, CuSCN, CuI, Cu2O, V2O5, WO3, CuS, MoO3, Co3O4, NiCo2O4, SrCO3, CuCrO2, CuScO2, CuGaO2 and graphene oxide.

7. The perovskite solar cell according to any one of claims 1 to 3, characterized in that: An interface modification layer is added between the perovskite photoactive layer and the electron transport layer, and / or between the perovskite photoactive layer and the hole transport layer, and the interface modification layer is selected from one or more of WO3, NiO, V2O5, MoO3, MoS2, TiO2, ZnO, LiF, Cs2CO3, CdS, SnO2 and graphene oxide; a blocking buffer layer is added between the hole transport layer and the top electrode layer, and / or between the electron transport layer and the top electrode layer, and the blocking buffer layer is selected from one or more of MoO3, Fe3O4, V2O5, Cu2O, NiO and ZnO.

8. The perovskite solar cell according to any one of claims 1 to 3, characterized in that: The thickness of the transparent conductive layer is 10-2000nm, the thickness of the electron transport layer is 10-200nm, the thickness of the perovskite photoactive layer is 300-800nm, the thickness of the hole transport layer is 10-200nm, and the thickness of the top electrode layer is 20-500nm.

9. The method for preparing a perovskite solar cell according to claim 1 or 2, characterized in that: The perovskite solar cell is a regular structure perovskite solar cell or a trans-structure trans-structure. The preparation method of the regular structure perovskite solar cell comprises the following steps: (1) sputtering a transparent conductive layer on a substrate using a planar target made of a conductive oxide by a magnetron sputtering method, using direct current or radio frequency sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixed gas, oxygen:argon=0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes (2) adding a reinforcing sheet to the outer layer of the planar target magnet, using a planar target made of a hole transport layer material, magnetron sputtering the hole transport layer on the transparent conductive layer, using DC or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixed gas, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (3) adding a weakening sheet to the outer layer of the planar target magnet, using an α-phase perovskite planar target made of a perovskite material, on the hole transport layer The perovskite photoactive layer is sputtered on the layer by radio frequency sputtering, the substrate temperature is 25°C-300°C, the sputtering power is 2-100W, the atmosphere is a hydrogen-argon mixed gas, hydrogen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 1-600 minutes; without any post-treatment, the α-phase perovskite photoactive layer can be obtained; (4) adding a reinforcing sheet to the outer layer of the planar target magnet, using a planar target made of an electron transport layer material, magnetron sputtering the electron transport layer on the perovskite photoactive layer, and using a direct current or RF sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixture, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (5) the top electrode layer is prepared by a magnetron sputtering method, using DC sputtering, the substrate temperature is room temperature, the sputtering power is 20-500W, the atmosphere is pure argon, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; that is, the formal structure perovskite solar cell is obtained.

10. The preparation method according to claim 9, characterized in that: The method for preparing an inverted perovskite solar cell comprises the following steps: (1) sputtering a transparent conductive layer on a substrate using a planar target made of a conductive oxide by a magnetron sputtering method, using direct current or radio frequency sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixed gas, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (2) adding a reinforcing sheet to the outer layer of the planar target magnet, using an electron transfer The electron transport layer is magnetron sputtered on the transparent conductive layer using a planar target made of a transport layer material, using direct current or radio frequency sputtering, the substrate temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixed gas, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (3) adding a weakening sheet to the outer layer of the planar target magnet, using an α-phase perovskite planar target made of a perovskite material, sputtering the perovskite photoactive layer on the electron transport layer, using radio frequency Sputtering, the substrate temperature is 25°C-300°C, the sputtering power is 2-100W, the atmosphere is a hydrogen-argon mixed gas, hydrogen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 1-600 minutes; without any post-treatment, an α-phase perovskite photoactive layer can be obtained; (4) adding a reinforcing sheet to the outer layer of the planar target magnet, using a planar target made of a hole transport layer material, magnetron sputtering the hole transport layer on the perovskite photoactive layer, using DC or RF sputtering, the substrate The temperature is room temperature, the sputtering power is 20-200W, the atmosphere is an oxygen-argon mixed gas, oxygen:argon = 0-20%, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; (5) the top electrode layer is prepared by a magnetron sputtering method, using DC sputtering, the substrate temperature is room temperature, the sputtering power is 20-500W, the atmosphere is pure argon, the sputtering pressure is 0.06-6Pa, and the sputtering time is 5-480 minutes; the inverted structure perovskite solar cell is obtained.

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