Film layer and preparation method thereof, and preparation method of perovskite cell

Abstract

The invention provides a film layer and a preparation method thereof, and a preparation method of a perovskite solar cell, and the preparation method of the film layer comprises the steps: inputting a medium-frequency alternating current to a twin target for sputtering, the material of the twin target comprises a metal oxide, and the conductivity of the metal oxide is greater than 2S / m; the atoms sputtered by the twin target are deposited on a substrate to form a film layer. According to the film layer and the preparation method thereof, and the preparation method of the perovskite solar cell provided by the invention, the preparation speed of the film layer can be improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of sputtering film coating, in particular to a film layer and a preparation method and a preparation method of a perovskite solar cell. BACKGROUND

[0002] The perovskite solar cell has the advantages of simple manufacturing process, low production cost and environmental friendliness and is widely applied to the fields of aviation, aerospace, military, agriculture and communication. As an important component of the perovskite solar cell, the hole transport layer has a great influence on the performance of the perovskite solar cell. The inorganic oxide film serves as an indispensable hole transport layer. Among them, nickel oxide is the most commonly used hole transport layer.

[0003] In the related art, the nickel oxide film is usually prepared by radio frequency magnetron sputtering. However, the speed of preparing the nickel oxide film by the radio frequency magnetron sputtering method is slow, which cannot meet the increasing production capacity demand. SUMMARY

[0004] Therefore, the application provides a film layer and a preparation method and a preparation method of a perovskite solar cell, which can improve the preparation speed of the film layer.

[0005] To solve the above technical problems, one technical scheme adopted by the application is to provide a preparation method of a film layer, comprising:

[0006] The intermediate frequency alternating current is input to the twin target for sputtering. The material of the twin target comprises a metal oxide, and the conductivity of the metal oxide is greater than 2 S / m.

[0007] The atoms sputtered by the twin target are deposited on the substrate to form the film layer.

[0008] According to an embodiment of the application, in the metal oxide, the molar ratio of the metal element to the oxygen element is 1:(0.6-0.9).

[0009] According to an embodiment of the application, the metal oxide comprises one or more of nickel oxide, cobalt oxide, chromium oxide, molybdenum oxide, vanadium oxide and tungsten oxide.

[0010] According to an embodiment of the application, the metal oxide is a doped metal oxide doped with a doping element. According to an embodiment of the application, the doping element comprises one or more of copper, magnesium, chromium, lithium, silver, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium.

[0011] According to an embodiment of the application, the intermediate frequency alternating current is input to the twin target for sputtering, comprising:

[0012] The twin targets are inputted with medium frequency alternating current for sputtering under the atmosphere of argon and oxygen; the oxygen flow percentage is 1.5% to 5.5% based on the total flow of argon and oxygen.

[0013] According to an embodiment of the present application, the twin targets and the substrate are placed in a reaction chamber, and the pressure of the reaction chamber is 0.1 Pa to 1.2 Pa.

[0014] According to an embodiment of the present application, the twin targets are inputted with medium frequency alternating current for sputtering, comprising:

[0015] The first permanent magnet is arranged between the twin targets, and the magnetic field strength of the first permanent magnet is 0.1 G to 100 G.

[0016] According to an embodiment of the present application, the twin targets are inputted with medium frequency alternating current for sputtering, comprising:

[0017] The second permanent magnet is arranged between the twin targets, and the second permanent magnet comprises a body and a metal shell surrounding the body, the metal shell is connected with the direct current positive electrode, and the magnetic field strength of the second permanent magnet is 0.1 G to 100 G.

[0018] According to an embodiment of the present application, the magnetic pole direction of the first permanent magnet is perpendicular to the axis direction of the twin targets.

[0019] And / or,

[0020] The magnetic pole direction of the second permanent magnet is perpendicular to the axis direction of the twin targets.

[0021] According to an embodiment of the present application, the voltage of the direct current positive electrode is 0.1 V to 100 V.

[0022] According to an embodiment of the present application, the twin targets comprise twin cylindrical targets or twin plane targets.

[0023] According to an embodiment of the present application, the power of the medium frequency alternating current is 5.5 KW to 16 KW.

[0024] The present application also provides a film layer, the film layer is prepared by the above-mentioned film layer preparation method, and the film layer is applied to a hole transport layer.

[0025] The present application also provides a preparation method of a perovskite battery, the preparation method of the perovskite battery comprises the above-mentioned film layer preparation method, and / or adopts the above-mentioned film layer.

[0026] The beneficial effects of the present application are: the metal oxide with conductivity greater than 2 S / m is used as the material of the twin target, because the twin target has a certain conductivity, so that the film can be prepared by sputtering the conductive twin target with medium frequency alternating current, so as to improve the preparation speed of the film. Because the two target bodies of the twin target are symmetrically arranged and alternately work, during the sputtering process, one target body is always in a high-efficiency sputtering state, compared with a single target system, the total amount of sputtered target atoms per unit time is higher. The medium frequency alternating current is periodically applied to the two target bodies of the twin target, that is, one target body is the cathode and the other target body is the anode, and the sputtering process can be continuously and stably carried out without frequent shutdown and cleaning of the target surface or waiting for the charge to dissipate, which is beneficial to improve the sputtering rate and in turn improve the preparation speed of the film. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0028] Figure 1 is a structural schematic diagram of the film preparation device provided by the embodiments of the present application.

[0029] Figure 2 is another structural schematic diagram of the film preparation device provided by the embodiments of the present application.

[0030] Figure 3 is a comparison diagram of the photoelectric conversion efficiency of the perovskite solar cells prepared in Example 1 to Example 6, Example 13 to Example 24 and Comparative Example 1 to Comparative Example 6.

[0031] Main figure mark explanation:

[0032] 1000 film preparation device, 100 twin target, 200 medium frequency alternating current source, 300 first permanent magnet. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0034] The terms "first", "second", "third", etc. in the present application are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features defined with "first", "second", "third" can explicitly or implicitly include at least one of the features. In the description of the present application, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise explicitly specified. All directional indications (such as up, down, left, right, front, back, etc.) in the embodiments of the present application are only used to explain the relative position relationship, movement condition, etc. between components in a certain posture (as shown in the drawings), and if the certain posture changes, the directional indications also change accordingly. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device that includes a series of steps or units is not limited to the listed steps or units, but can optionally include steps or units not listed, or can optionally include other steps or units inherent to the process, method, product or device.

[0035] Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment can be included in at least one embodiment of the application. The appearance of the phrase in various places in the specification does not necessarily all refer to the same embodiment, nor is it necessarily independent or alternative embodiments to each other. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0036] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, which means that there can be three relationships, for example, A and / or B, which can represent the three cases of A alone, A and B together, and B alone. In addition, the character " / " in this paper generally represents that the front and rear associated objects are a "or" relationship.

[0037] In the description of the embodiments of the present application, the technical terms "vertical", "horizontal", "inner", "outer", etc. indicate the orientation or position relationship based on the orientation or position relationship shown in the drawings, which is only for the convenience of describing the embodiments of the present application and simplifying the description, and does not indicate or imply that the indicated device or element must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the embodiments of the present application.

[0038] In the description of the embodiments of the present application, unless otherwise explicitly specified and limited, the technical terms "mount", "connect", "connect", "fix" and other terms should be understood in a broad sense, for example, can be fixedly connected, or can be detachably connected, or can be integrated; can be mechanically connected, or can be electrically connected; can be directly connected, or can be indirectly connected through an intermediate medium; can be the internal communication of two elements or the interaction relationship of two elements. For those skilled in the art, the specific meaning of the above terms in the embodiments of the present application can be understood according to the specific circumstances.

[0039] In the related art, a nickel oxide film is usually prepared by radio frequency magnetron sputtering, but the speed of preparing the nickel oxide film by the radio frequency magnetron sputtering is slow, which cannot meet the increasing production capacity demand.

[0040] To solve the above technical problems, one technical scheme adopted by the present application is to provide a film layer preparation method, comprising: inputting medium frequency alternating current to a twin target for sputtering, the material of the twin target comprising a metal oxide, the conductivity of the metal oxide being greater than 2 S / m; and depositing atoms sputtered by the twin target on a substrate to form a film layer.

[0041] In the technical scheme of the embodiments of the present application, the metal oxide with a conductivity greater than 2 S / m is used as the material of the twin target, and since the twin target has a certain conductivity, the medium frequency alternating current can be used to sputter the conductive twin target for film preparation, so as to improve the film preparation speed. This is because the two target bodies of the twin target are symmetrically arranged and alternately operated, and in the sputtering process, one target body is always in a high-efficiency sputtering state. Compared with a single target system, the total amount of sputtered target atoms per unit time is higher. The medium frequency alternating current is periodically applied to the two target bodies of the twin target, that is, one target body is a cathode and the other target body is an anode. The sputtering process can be continuously and stably performed without frequent shutdown for cleaning the target surface or waiting for charge dissipation, which is beneficial to improve the sputtering rate and further improve the film preparation speed.

[0042] Please refer to Figure 1 , Figure 1 is a structural schematic diagram of a film layer preparation device provided by the embodiments of the present application, and the film layer preparation method provided by the embodiments of the present application is realized by the film layer preparation device 1000. The film layer preparation device 1000 comprises a twin target 100 and a medium frequency alternating current source 200. The twin target 100 comprises two independent target bodies, and the two target bodies are arranged in a parallel and symmetric manner. The output end of the medium frequency alternating current source 200 is electrically connected with the two target bodies of the twin target 100, and is used for applying medium frequency alternating current to the target bodies. The two target bodies of the twin target 100 are cathode and anode to each other in the sputtering process, and the polarity is periodically switched by the medium frequency alternating current source 200, which can suppress the arc on the target surface, is beneficial to improve the sputtering rate, and further improves the film preparation speed.

[0043] In the embodiments of the present application, the substrate can be placed on a carrier, and the thickness of the film layer can be controlled by changing the moving speed of the carrier. The substrate includes, but is not limited to, quartz glass, monocrystalline silicon wafer, etc., and the user can select according to actual needs.

[0044] According to an embodiment of the present application, the molar ratio of the metal element and the oxygen element in the metal oxide is 1:(0.6-0.9). By adjusting the molar ratio of the metal element and the oxygen element in the metal oxide, the metal oxide has a conductive property, and the preparation speed of the film layer can be significantly improved by cooperating with the intermediate frequency alternating current. In addition, the molar ratio of the metal element and the oxygen element in the metal oxide is in the above range, which can also make the adjustable range of the oxygen content in the prepared film layer wider, thereby being beneficial to the regulation of the quality of the film layer. The molar ratio of the metal element and the oxygen element can be 1:0.6, 1:0.7, 1:0.8, 1:0.9, etc., or a range value composed of any two of the above values, for example, 1:0.6-1:0.7, 1:0.7-1:0.8, 1:0.8-1:0.9, etc.

[0045] According to an embodiment of the present application, the metal oxide includes one or more of nickel oxide, cobalt oxide, chromium oxide, molybdenum oxide, vanadium oxide, and tungsten oxide.

[0046] According to an embodiment of the present application, the metal oxide is a doped metal oxide doped with a doping element. By doping the metal oxide, the metal oxide can meet the conductivity requirement of intermediate frequency alternating sputtering.

[0047] According to an embodiment of the present application, the doping element includes one or more of copper, magnesium, chromium, lithium, silver, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.

[0048] According to an embodiment of the present application, the intermediate frequency alternating current is input to the twin target for sputtering, which includes:

[0049] In an argon and oxygen atmosphere, the intermediate frequency alternating current is input to the twin target 100 for sputtering; based on the total flow rate of argon and oxygen, the flow rate percentage of oxygen is 1.5%-5.5%. The argon is ionized under the action of the electric field to form Ar + , Ar +The twin target 100 is bombarded so that the metal atoms sputtered from the twin target 100 are deposited on the substrate to form a film layer. Oxygen and the sputtered metal atoms chemically react on the surface of the substrate to form a metal oxide film layer with a desired stoichiometric ratio. By adjusting the flow percentage of oxygen to be in the above range, on the one hand, it is beneficial to form a metal oxide film layer with a desired stoichiometric ratio; on the other hand, it can maintain the efficient sputtering of metal atoms in the twin target 100, thereby maintaining the preparation speed of the film layer. Among them, based on the total flow of argon and oxygen, the flow percentage of oxygen can be 1.5%, 2.5%, 3.5%, 4.5%, 5.5%, or a range value composed of any two of the above values, for example, 1.5%~2.5%, 2.5%~3.5%, 3.5%~4.5%, 4.5%~5.5%, etc.

[0050] According to an embodiment of the present application, the twin target and the substrate are placed in a reaction chamber, and the pressure of the reaction chamber is 0.1Pa~1.2Pa. By adjusting the pressure of the reaction chamber to be in the above range, on the one hand, it can make the ionization efficiency of argon + be relatively high, so that the sputtering rate of the twin target 100 is increased, thereby increasing the preparation speed of the film layer; on the other hand, it reduces the risk of too high collision frequency of sputtered atoms and gas molecules to reduce the deposition rate of target atoms. Among them, the pressure of the reaction chamber can be 0.1Pa, 0.5Pa, 0.9Pa, 1.2Pa, or a range value composed of any two of the above values, for example, 0.1Pa~0.5Pa, 0.5Pa~0.9Pa, 0.9Pa~1.2Pa, etc.

[0051] According to an embodiment of the present application, the twin target 100 is inputted with intermediate frequency alternating current for sputtering, which includes: the first permanent magnet 300 is arranged between the twin targets 100, and the magnetic field strength of the first permanent magnet 300 is 0.1G~100G. The back of the twin target 100 is provided with a permanent magnet array to form a specific form of closed magnetic field, which is parallel to the target surface of the twin target 100 and in the shape of a circular track for constraining the motion of secondary electrons. The magnetic field generated by the first permanent magnet 300 arranged between the twin targets 100 is superimposed with the magnetic field of the twin target 100, the total magnetic field strength and the magnetic field range are expanded, the spiral motion path of the secondary electrons is lengthened, the collision probability of the secondary electrons with argon is increased, and more Ar + , Ar + is generated, the sputtering of the twin target 100 is enhanced, and the preparation speed of the film layer is further improved. It should be noted that when Ar +When the surface of the twin target 100 is bombarded, in addition to sputtering the atoms of the target, electrons are also knocked out of the twin target 100, which are called secondary electrons. The magnetic field strength of the first permanent magnet 300 can be 0.1G, 10G, 40G, 70G, 100G, or a range value composed of any two of the above values, for example, 0.1G-10G, 10G-40G, 40G-70G, 70G-100G, etc.

[0052] Please refer to Figure 2 , Figure 2 is another structural schematic diagram of the film layer preparation device provided by the embodiment of the present application. The film layer preparation method provided by the embodiment of the present application is realized by the film layer preparation device 1000. The film layer preparation device 1000 comprises a twin target 100, a medium-frequency alternating current power supply 200 and a first permanent magnet 300. The twin target 100 comprises two target bodies which are independent of each other and are arranged in a parallel and symmetrical manner. The first permanent magnet 300 is arranged between the two target bodies. The output end of the medium-frequency alternating current power supply 200 is electrically connected to the two target bodies of the twin target 100, and is used to apply a medium-frequency alternating current to the target bodies.

[0053] According to an embodiment of the present application, the medium-frequency alternating current is input to the twin target 100 for sputtering, comprising: a second permanent magnet is arranged between the twin target 100. The second permanent magnet comprises a body and a metal shell surrounding the body. The metal shell is connected to a direct-current positive voltage. The magnetic field strength of the second permanent magnet is 0.1G-100G. When the metal shell applies a direct-current positive voltage, the negatively charged secondary electrons are attracted by the Coulomb force. The motion of the secondary electrons changes from a pure magnetic constraint spiral trajectory to a directional acceleration motion driven by an electric field. The electric field force makes the secondary electrons fly radially from the vicinity of the target surface to the metal shell. The motion path is increased (the original magnetic field constraint path is limited to the target surface region). The collision probability of the secondary electrons with argon gas is increased, and more Ar + and secondary electrons are generated. + The bombardment of the target material is enhanced, and thus the preparation speed of the film layer is improved. The magnetic field strength of the second permanent magnet can be 0.1G, 10G, 40G, 70G, 100G, or a range value composed of any two of the above values, for example, 0.1G-10G, 10G-40G, 40G-70G, 70G-100G, etc.

[0054] According to an embodiment of the present application, the magnetic pole direction of the first permanent magnet is perpendicular to the axis direction of the twin target; and / or, the magnetic pole direction of the second permanent magnet is perpendicular to the axis direction of the twin target. By arranging the magnetic pole direction of the first permanent magnet and the second permanent magnet to be perpendicular to the axis direction of the twin target, the magnetic field generated by the first permanent magnet or the second permanent magnet can be superimposed with the magnetic field of the twin target. The total magnetic field strength and the magnetic field range are expanded. The spiral motion path of the secondary electrons is lengthened. The collision probability of the secondary electrons with argon gas is increased. More Ar +, Ar + The bombardment of the twin target 100 enhances sputtering, thereby improving the preparation speed of the film layer.

[0055] According to an embodiment of the present application, the voltage of the direct current positive electricity is 0.1V-100V. By regulating the voltage of the direct current positive electricity to be in the above range, the motion of the secondary electrons is changed from the pure magnetic constraint spiral trajectory to the electric field driven directional acceleration motion, the collision probability of the secondary electrons with argon is increased, and more Ar + and secondary electrons are generated. + The bombardment of the target enhances sputtering, thereby improving the preparation speed of the film layer. The voltage of the direct current positive electricity can be 0.1V, 10V, 30V, 50V, 70V, 100V, or a range value composed of any two of the above values, such as 0.1V-10V, 10V-30V, 30V-50V, 50V-70V, 70V-100V, etc.

[0056] According to an embodiment of the present application, the twin target 100 includes a twin cylindrical target or a twin planar target. The twin cylindrical target includes two cylindrical target bodies arranged side by side, and the two cylindrical target bodies rotate around the central axis, which can uniformly etch the surface of the cylindrical target body and improve the utilization rate of the target body. The twin planar target includes two planar target bodies arranged side by side, and the planar target body does not need to rotate, which reduces the mechanical vibration and the periodic change of the magnetic field caused by rotation, thereby making the plasma distribution more stable and helping to improve the repeatability of the sputtering process and the uniformity of the film layer.

[0057] According to an embodiment of the present application, the power of the intermediate frequency alternating current is 5.5KW-16KW. By regulating the power of the intermediate frequency alternating current to be in the above range, on the one hand, the argon can be fully ionized to generate Ar + , the density of Ar + is increased, the sputtering rate is improved, and thus the preparation speed of the film layer is improved; on the other hand, the risk of triggering the melting pits due to the excessively high local power density of the target surface is reduced. The power of the intermediate frequency alternating current can be 5.5KW, 8KW, 11KW, 13KW, 16KW, or a range value composed of any two of the above values, such as 5.5KW-8KW, 8KW-11KW, 11KW-13KW, 13KW-16KW, etc.

[0058] The present application also provides a film layer, which is prepared by the above-mentioned method for preparing a film layer and is applied to a hole transport layer.

[0059] The present application also provides a preparation method of a perovskite battery, which includes the above-mentioned method for preparing a film layer and / or uses the above-mentioned film layer.

[0060] The beneficial effects of the present application are further illustrated by the following examples.

[0061] In order to make the technical problems, technical solutions and beneficial effects solved by the embodiments of the present application clearer, the following will be further described in detail in combination with the embodiments and drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative, but not as any limitation on the present application and its application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0062] Embodiment 1

[0063] 1) Preparation of the film layer

[0064] The plating chamber was evacuated to a pressure of ≤5×10 -4 Pa, and a mixed gas of argon and oxygen was introduced into the reaction chamber, and the pressure of the reaction chamber was controlled to be 0.2 Pa, wherein the flow percentage of oxygen was 1.40% based on the total flow of argon and oxygen.

[0065] The twin cylindrical target was inputted with medium frequency alternating current for pre-sputtering, and the material of the twin cylindrical target was NiO 0.8 with an electrical conductivity of 100 S / m. The pre-sputtering power was linearly and uniformly increased from 0 KW to the process power of 5.5 KW, and the rising time was 2 hours.

[0066] The carrier supporting the substrate was uniformly moved at a speed of 16 mm / s, so that the substrate passed through the sputtering area of the twin cylindrical target, and the substrate was plated during the movement. When the moving distance of the carrier reached 1900 mm, the substrate moved out of the sputtering area, and a film layer with a thickness of 29.7 mm was obtained.

[0067] After the plating process was completed, the power supply to the twin cylindrical target was stopped, the mixed gas was cut off, and the plated substrate was taken out.

[0068] 2) Preparation of the perovskite solar cell

[0069] A first electrode layer was prepared on a glass substrate;

[0070] A hole transport layer was prepared on the first electrode layer, wherein the hole transport layer was a film layer prepared by the method for preparing the film layer in step 1);

[0071] A perovskite layer was prepared on the hole transport layer;

[0072] An electron transport layer was prepared on the perovskite layer;

[0073] A second electrode was prepared on the electron transport layer.

[0074] Embodiments 2 and 3

[0075] Example 2, Example 3 differ from Example 1 in that the pressure of the reaction chamber is different.

[0076] Example 4

[0077] Example 4 differs from Example 1 in that the percentage of oxygen flow based on the total flow of argon and oxygen is different, and the moving speed of the carrier is different.

[0078] Example 5 and Example 6

[0079] Example 5, Example 6 differ from Example 4 in that the pressure of the reaction chamber is different.

[0080] Example 7

[0081] Example 7 differs from Example 1 in that the power of the intermediate frequency alternating current is different, and the moving speed of the carrier is different.

[0082] Example 8 and Example 9

[0083] Example 8, Example 9 differ from Example 7 in that the pressure of the reaction chamber is different.

[0084] Example 10

[0085] Example 10 differs from Example 7 in that the percentage of oxygen flow based on the total flow of argon and oxygen is different, and the moving speed of the carrier is different.

[0086] Example 11 and Example 12

[0087] Example 11, Example 12 differ from Example 10 in that the pressure of the reaction chamber is different.

[0088] Example 13

[0089] Example 13 and Example 1 differ in that a first permanent magnet is arranged between the twin cylindrical targets, and the magnetic field strength of the first permanent magnet is 50G.

[0090] Example 14 and Example 15

[0091] Example 14, Example 15 differ from Example 13 in that the pressure of the reaction chamber is different.

[0092] Example 16

[0093] Example 16 differs from Example 13 in that the percentage of oxygen flow based on the total flow of argon and oxygen is different, and the moving speed of the carrier is different.

[0094] Example 17 and Example 18

[0095] Example 17, Example 18 and Example 16 differ in that the pressure of the reaction chamber is different.

[0096] Example 19

[0097] Example 19 and Example 1 differ in that a second permanent magnet is arranged between the twin cylindrical targets, the second permanent magnet comprising a body and a metal shell surrounding the body, the metal shell being connected to the direct current positive electricity, the magnetic field strength of the second permanent magnet being 50 G, and the voltage of the direct current positive electricity being 50 V.

[0098] Example 20 and Example 21

[0099] Example 20, Example 21 and Example 19 differ in that the pressure of the reaction chamber is different.

[0100] Example 22

[0101] Example 22 and Example 19 differ in that the percentage of the flow rate of oxygen based on the total flow rate of argon and oxygen is different, and the moving speed of the carrier is different.

[0102] Example 23 and Example 24

[0103] Example 23, Example 24 and Example 22 differ in that the pressure of the reaction chamber is different.

[0104] Comparative Example 1

[0105] Comparative Example 1 and Example 1 differ in that the radio frequency electricity is input to the planar single target for pre-sputtering.

[0106] Comparative Example 2 and Comparative Example 3

[0107] Comparative Example 2 and Comparative Example 3 and Comparative Example 1 differ in that the pressure of the reaction chamber is different.

[0108] Comparative Example 4

[0109] Comparative Example 4 and Comparative Example 1 differ in that the percentage of the flow rate of oxygen based on the total flow rate of argon and oxygen is different, and the moving speed of the carrier is different.

[0110] Comparative Example 5 and Comparative Example 6

[0111] Comparative Example 5 and Comparative Example 6 and Comparative Example 4 differ in that the pressure of the reaction chamber is different.

[0112] The specific method for testing the relevant parameters is as follows:

[0113] 1) The testing method for the film coating rate.

[0114] Film coating rate = film thickness / (carrier moving distance / carrier moving speed)

[0115] 2) Photovoltaic conversion efficiency test of perovskite solar cells.

[0116] Under normal temperature and pressure, using a standard AM1.5G solar light source as a simulated sunlight source, the current-voltage characteristic curves of the perovskite solar cells prepared in Examples 1-6, Examples 13-24, and Comparative Examples 1-6 were measured using a four-channel digital source meter (Keithley 2400) under the illumination of the light source. Voc (open-circuit voltage, V) and Jsc (short-circuit current density, mA / cm²) were obtained. 2 ), FF (fill factor), PCE (photoelectric conversion efficiency) = (Voc × Jsc × FF) / 100.

[0117] Table 1. Preparation process parameters of the film layer in the examples and comparative examples.

[0118]

[0119]

[0120] 1) In Examples 1 to 24, sputtering was performed by inputting intermediate frequency alternating current to a twin target; in Comparative Examples 1 to 6, sputtering was performed by inputting radio frequency current to a planar single target. As can be seen from the data in Table 1, under the same conditions (same power for intermediate frequency alternating current and radio frequency current, same pressure in the reaction chamber, and the same percentage of oxygen flow based on the total flow rate of argon and oxygen), the deposition rate of Examples 1 to 24 was greater than that of Comparative Examples 1 to 6. This indicates that, compared to sputtering with radio frequency current input to a planar single target, sputtering with intermediate frequency alternating current input to a twin target can improve the deposition rate, thereby increasing the film preparation speed.

[0121] 2) Compared to Examples 1-6, under the same conditions (same power of medium-frequency AC and radio-frequency AC, same pressure in the reaction chamber, same total flow rate of argon and oxygen, and same percentage of oxygen flow), the plating rate of Examples 13-18 is better than that of Examples 1-6. This is because, in Examples 13-18, a first permanent magnet is placed between the cylindrical targets. The magnetic field generated by the first permanent magnet is superimposed on the magnetic field of the twin targets, expanding the total magnetic field strength and range, lengthening the spiral motion path of secondary electrons, increasing the probability of collision between secondary electrons and argon, and generating more Ar. + Ar + Bombardment twin target sputtering is enhanced, which can improve the deposition rate and thus increase the film preparation speed.

[0122] 3) Compared with Examples 13-18, the plating rates of Examples 19-24 are superior to those of Examples 13-18 under the same conditions (the same power of the intermediate frequency alternating current and the power of the radio frequency alternating current, the same pressure of the reaction chamber, and the same total flow rate of argon and oxygen and the same percentage of the flow rate of oxygen). This is because, in Examples 19-24, the second permanent magnet is arranged between the cylindrical targets, the second permanent magnet comprises a body and a metal shell surrounding the body, the metal shell is connected with the direct current positive electricity, when the metal shell applies the direct current positive voltage, the negatively charged secondary electrons are attracted by the coulomb force, the movement of the secondary electrons changes from the pure magnetic constraint spiral trajectory to the directional acceleration movement driven by the electric field, the electric field force makes the secondary electrons fly radially from the target surface to the metal shell, the movement path is increased (the original magnetic field constraint path is limited to the target surface area), the collision probability of the secondary electrons with argon is increased, more Ar + and secondary electrons are generated, the Ar + target sputtering is enhanced, and therefore the plating rate can be improved, and the preparation speed of the film layer is further improved.

[0123] 4) Figure 3 is a comparison chart of the photoelectric conversion efficiencies of the perovskite solar cells prepared in Examples 1-6, Examples 13-24 and Comparative Examples 1-6 of the present application. From Figure 3 It can be seen that the photoelectric conversion efficiency of the perovskite solar cell prepared by the present scheme can be maintained at the same level as that of the perovskite solar cell prepared in Comparative Examples 1-6, and the photoelectric conversion efficiency of the perovskite solar cell prepared in some examples is even superior to that of the perovskite solar cell prepared in Comparative Examples 1-6.

[0124] The above is only an embodiment of the present application, and does not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation using the content of the specification and drawings, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for producing a film layer, characterized by, The method comprises: inputting middle frequency alternating current to the twin targets for sputtering, the material of the twin targets comprising metal oxide, the conductivity of the metal oxide being greater than 2 S / m; forming a film layer on a substrate by atom deposition of sputtering of the twin targets.

2. The method of claim 1, wherein In the metal oxide, the molar ratio of metal element to oxygen element is 1:(0.6-0.9).

3. The method of claim 2, wherein the film layer is prepared by a method comprising: The metal oxide comprises one or more of nickel oxide, cobalt oxide, chromium oxide, molybdenum oxide, vanadium oxide, tungsten oxide.

4. The method of claim 1, wherein The metal oxide is a doped metal oxide doped with a doping element.

5. The method of claim 4, wherein the film layer is prepared by a method comprising: The doping element comprises one or more of copper, magnesium, chromium, lithium, silver, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium.

6. The method of claim 1, wherein The inputting middle frequency alternating current to the twin targets for sputtering comprises: inputting middle frequency alternating current to the twin targets for sputtering under the atmosphere of argon and oxygen, the flow percentage of the oxygen being 1.5%-5.5% based on the total flow of the argon and the oxygen.

7. The method of claim 1, wherein The twin targets and the substrate are placed in a reaction chamber, the pressure of the reaction chamber being 0.1 Pa-1.2 Pa.

8. The method of claim 1, wherein The inputting middle frequency alternating current to the twin targets for sputtering comprises: A first permanent magnet is arranged between the twin targets, the magnetic field strength of the first permanent magnet being 0.1 G-100 G.

9. The method of claim 1, wherein The inputting middle frequency alternating current to the twin targets for sputtering comprises: A second permanent magnet is arranged between the twin targets, the second permanent magnet comprising a body and a metal shell surrounding the body, the metal shell being connected with direct current positive electricity, the magnetic field strength of the second permanent magnet being 0.1 G-100 G.

10. The method of claim 8 or 9, wherein The pole direction of the first permanent magnet is perpendicular to the axis direction of the twin targets; and / or, The pole direction of the second permanent magnet is perpendicular to the axis direction of the twin targets.

11. The method of claim 9, wherein the film layer is prepared by a method comprising: The voltage of the direct current positive electricity is 0.1 V-100 V.

12. The method of claim 1, wherein The twin targets comprise twin cylindrical targets or twin plane targets.

13. The method of claim 1, wherein The power of the middle frequency alternating current is 5.5 KW-16 KW.

14. A film layer prepared by the method for preparing a film layer according to any one of claims 1-13, the film layer being applied to a hole transport layer.

15. A method of producing a perovskite cell, characterized by, The method for preparing a perovskite battery comprises the method for preparing a film layer according to any one of claims 1-13, and / or the film layer according to claim 14 is used.

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