A magnetron sputtering device and its fabrication method for perovskite solar cells

Abstract

This invention discloses a magnetron sputtering device and preparation method specifically for perovskite solar cells, relating to the field of solar cell manufacturing technology. The device includes a first chamber, a second chamber, a third chamber, a fourth chamber, a fifth chamber, a sixth chamber, a seventh chamber, and an eighth chamber. Through the provided vertical rotating magnetron sputtering coating pilot line, a full-process magnetron sputtering preparation method is used to prepare all-inorganic perovskite solar cells. It can also provide services for organic perovskite solar cells and inorganic-organic hybrid perovskite solar cells. By designing a novel plasma chamber and co-sputtering coating chamber layout, along with a matching transmission system and power system, a continuous magnetron sputtering coating process can be achieved, greatly simplifying the preparation process, reducing preparation costs, effectively reducing the area required, improving production efficiency, and simplifying the equipment complexity of the coating production line.

Description

Technical Field

[0001] This invention relates to the field of solar cell manufacturing technology, specifically to a magnetron sputtering device and preparation method for perovskite solar cells. Background Technology

[0002] Photovoltaic power generation is one of the most promising energy sources for alleviating the energy crisis and replacing fossil fuels. Perovskite is a new and promising type of photovoltaic cell, mainly made of perovskite materials, and has high photoelectric conversion efficiency.

[0003] The fabrication of perovskite solar cells mainly employs a hybrid organic-inorganic approach, using alternating physical and chemical methods. Among these methods, magnetron sputtering is a commonly used fabrication method. It achieves precise control of the thin film by using a magnetic field in a vacuum environment to control the movement of electrons in the plasma.

[0004] Current methods for fabricating perovskite solar cells primarily employ magnetron sputtering, which uses a magnetic field in a vacuum environment to control the movement of electrons within the plasma, thereby achieving precise control over the thin film. This method can produce perovskite thin films with uniform thickness and good performance.

[0005] However, the main problem with this method is the complexity of the preparation process, which requires multiple alternating physical and chemical methods. This not only increases the preparation cost but also prolongs the preparation time. Although magnetron sputtering equipment can produce high-quality perovskite thin films, existing preparation methods still have some problems. First, the complexity of the preparation process leads to high preparation costs, which is a huge challenge for large-scale production. Second, the need to alternate between physical and chemical methods during the preparation process not only prolongs the preparation time but also reduces production efficiency. In addition, existing preparation methods cannot effectively guarantee the overall uniformity and performance of thin-film solar cells, which may affect the performance and stability of solar cells. Based on this, a magnetron sputtering device and preparation method specifically for perovskite solar cells are proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a magnetron sputtering device and preparation method for perovskite solar cells, which solves the technical problem that the preparation process requires multiple alternating physical and chemical methods, which not only prolongs the preparation time but also reduces production efficiency.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A magnetron sputtering device and its fabrication method for perovskite solar cells include the following steps:

[0009] Step 1: Transfer the electro-glass substrate to be processed from the first sample holder to the first chamber, and turn on the radio frequency ion source to clean the impurities on the substrate surface;

[0010] Step 2: The cleaned conductive glass substrate is transported to the second chamber through a valve for sputtering deposition to prepare a hole transport layer;

[0011] Step 3: Transfer the prepared hole transport layer into the third chamber for co-sputtering deposition to prepare the perovskite absorber layer;

[0012] Step 4: The prepared perovskite absorber layer is transferred to the fourth chamber. After being rotated and adjusted by the sample holder magnetic rotation device, the substrate is transferred to the fifth chamber.

[0013] Step 5: Co-sputter coating is performed on the substrate in the fifth chamber to prepare the electron transport layer;

[0014] Step 6: Transfer the prepared electron transport layer to the sixth chamber for sputtering deposition to prepare a SnO2:In2O3 thin film;

[0015] Step 7: Transfer the prepared SnO2:In2O3 thin film to the seventh chamber for sputtering deposition to prepare an AgCu alloy thin film as the top electrode;

[0016] Step 8: Transfer the prepared AgCu alloy thin film to the eighth chamber to complete the fabrication of the perovskite solar cell.

[0017] As a further aspect of the present invention, the specific method for obtaining the hole transport layer is as follows:

[0018] The cleaned substrate is transferred to the second chamber for coating. Before coating, the chamber is evacuated to a certain background vacuum level. Then, the RF power supplies T1 and T2 are set, and the corresponding targets are installed. By adjusting the angle between the target cathode and the pilot line, sputtering gas and reactive gas are introduced for co-sputtering. Finally, the power is turned off, and the chamber is heated to a certain temperature and maintained for a period of time to prepare NiO. x -V thin film serves as a hole transport layer.

[0019] As a further aspect of the present invention, the specific method for preparing the perovskite absorber layer is as follows:

[0020] Before coating, the chamber was evacuated, and then the RF power of T3 and T4 was set. The corresponding target materials were installed. By adjusting the angle between the target cathode and the pilot line, sputtering gas and reactive gas were introduced for co-sputtering. After the sputtering power was turned off, the electron cyclotron resonance source was kept on for a period of time to stabilize the absorption layer structure. Finally, CsPbI2Br-Sn thin film was prepared as a perovskite absorption layer.

[0021] As a further aspect of the present invention, the specific method for preparing the electron transport layer is as follows:

[0022] The CsPbI₂Br-Sn thin film was placed in the fifth chamber, and a vacuum was first drawn to 3 × 10⁻⁴ Pa. Then, the T5 RF power supply was set to 200 W for the W target and the T6 RF power supply to 30 W for the Ti target. The positions of the W and Ti targets were adjusted to form an 85° angle with the substrate, and co-sputtering was started. Ar and O₂ were used as the sputtering gas and reactant gas, respectively, to prepare WO₂ using the co-sputtering method. X -Ti thin film as electron transport layer.

[0023] As a further aspect of the present invention, the specific method for preparing SnO2:In2O3 thin films is as follows:

[0024] Will WO X -Ti thin films were transferred to the sixth chamber, and the RF power was set to 100W. SnO2:In2O3 = 99:1 target material was used for sputtering to form SnO2:In2O3 thin films with a thickness of 15-60nm.

[0025] As a further aspect of the present invention, the specific method for preparing the AgCu alloy thin film is as follows:

[0026] The SnO2:n2O3 thin film was transferred to the seventh chamber, the radio frequency power was set to 50W, and AgCu alloy thin film was prepared by sputtering using an Ag:Cu=98:2 alloy target.

[0027] As a further aspect of the present invention: a magnetron sputtering device for perovskite solar cells for performing the method includes a chamber body, wherein the chamber is divided into a first chamber, a second chamber, a third chamber, a fourth chamber, a fifth chamber, a sixth chamber, a seventh chamber, and an eighth chamber by a plurality of valves arranged in sequence;

[0028] A first sample rack is provided on the outside of the first chamber, and a second feed rack is provided on the outside of the eighth chamber;

[0029] The first chamber is equipped with a radio frequency ion source, the second and third chambers are each equipped with two radio frequency power sources, the third chamber is also equipped with an electron cyclotron resonance source, the fourth chamber is equipped with a sample holder magnetic rotation device, the fifth chamber is equipped with two radio frequency power sources and a plasma source, the sixth chamber is equipped with a planar target, a radio frequency power source and an ion source, and the seventh chamber is equipped with a planar target and a radio frequency power source.

[0030] As a further embodiment of the present invention: the first chamber is a plasma chamber, the second chamber is a sputtering coating chamber, the third chamber is a co-sputtering coating chamber, the fourth chamber is a buffer rotating chamber, the fifth chamber is a sputtering coating chamber, the sixth chamber is a coating chamber, the seventh chamber is a coating chamber, and the eighth chamber is a buffer chamber.

[0031] As a further embodiment of the present invention: the first chamber and the second chamber are jointly equipped with a mechanical pump and a Roots pump, and the second chamber is equipped with a molecular pump; the third chamber is equipped with a mechanical pump, a Roots pump and a molecular pump; the fourth chamber is equipped with a mechanical pump; the fifth chamber, the sixth chamber, the seventh chamber and the eighth chamber are jointly equipped with a mechanical pump and a Roots pump, and the sixth chamber, the seventh chamber and the eighth chamber are jointly equipped with a molecular pump.

[0032] As a further aspect of the present invention: a chamber heater is provided in both the second and fourth chambers, and a reciprocating conveying device is provided in the first, second, third, fourth, fifth, sixth, seventh, and eighth chambers.

[0033] The beneficial effects of this invention are:

[0034] (1) The present invention provides a vertical rotating magnetron sputtering coating pilot line, which can be used to prepare all-inorganic perovskite batteries using a full-process magnetron sputtering preparation method. It can also provide services for organic perovskite batteries and inorganic-organic hybrid perovskite batteries. At the same time, by designing a new plasma chamber and co-sputtering coating chamber layout, as well as a matching transmission system and power system, a continuous magnetron sputtering coating process can be realized, which greatly simplifies the preparation process, reduces the preparation cost, effectively reduces the area used, and improves production efficiency. Compared with conventional magnetron sputtering equipment, it can reduce the number of vacuum pumping devices, simplify the equipment complexity of the coating production line, and reduce equipment costs.

[0035] (2) The present invention improves the uniformity and performance of thin films: By optimizing the design and layout of the target material and adjusting the sputtering parameters, the present invention can achieve precise control over the thickness and performance of thin films, effectively improving the overall uniformity and performance of thin film solar cells, thereby improving the performance and stability of solar cells;

[0036] (3) By using multiple radio frequency power supplies and plasma power supplies, the present invention can use ion source-assisted magnetron sputtering to prepare thin films in a low electron beam energy, high ionization environment, reducing sputtering damage, ion damage, etc., without affecting the density of the underlying thin film.

[0037] (4) By designing multiple co-sputtering coating chambers and buffer rotating chambers, each chamber is isolated and the environment is independent, realizing the separation of different atmospheres and high and low temperatures. Multiple batches of coating operations can be carried out at the same time, which improves the utilization rate of the equipment and further improves the production efficiency.

[0038] (5) The present invention, by designing the same target cathode size, can achieve angle adjustment by rotation and tilting, and can also be transformed into a planar target for individual sputtering, thereby flexibly adapting to a variety of different target materials and improving the versatility and applicability of the equipment. Attached Figure Description

[0039] The invention will now be further described with reference to the accompanying drawings.

[0040] Figure 1 This is a schematic diagram of the method framework structure of the present invention;

[0041] Figure 2 This is a schematic diagram of the vertical rotating magnetron sputtering coating pilot line of the present invention;

[0042] Figure 3 This is the IV curve of the perovskite solar cell of Embodiment 1 of the present invention;

[0043] Figure 4 This is the IV curve of the perovskite solar cell of Embodiment 2 of the present invention;

[0044] In the diagram: CB1, first chamber; CB2, second chamber; CB3, third chamber; CB4, fourth chamber; CB5, fifth chamber; CB6, sixth chamber; CB7, seventh chamber; CB8, eighth chamber; 1, first sample holder; 2, mechanical pump; 3, Roots pump; 4, molecular pump; 5, cathode; 6, sample holder magnetic rotation device; 7, gate valve; 8, second feed rack; T1-T8: target material. Detailed Implementation

[0045] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0046] Example 1

[0047] Please see Figures 1-3 As shown, this invention provides a method for fabricating perovskite solar cells, comprising the following steps:

[0048] Step 1: Transfer the ITO conductive glass substrate to be processed, located on the first sample holder 1, to the first chamber. The first chamber is a plasma chamber. Turn on the radio frequency (RF) ion source in the first chamber and set its power to 300W and the time to 20 minutes to achieve the purpose of cleaning impurities on the substrate surface.

[0049] Step 2: The cleaned conductive glass substrate is transported to the second chamber via a valve. The second chamber is the sputtering deposition chamber. Before the conductive glass substrate is deposited in the second chamber, a vacuum of 3×10⁻⁶ is evacuated to the background vacuum level. -4 Pa, set the RF power of T1 to 100W, then install T1 as a Ni target and T2 as a V target, and set the RF power of T2 to 10W.

[0050] Then, the rotation device located in the second chamber is activated, and the vertical angle between the cathodes of targets T1 and T2 and the pilot line is adjusted to 75 degrees. High-purity argon (Ar) is then introduced into the second chamber as the sputtering gas, and the plasma power supply is connected to high-purity oxygen (O2) as the reactant gas to ensure complete ionization for co-sputtering (alternatively, the plasma power supply and the T2 RF power supply can be connected together to the T2 cathode to fully ionize the metal V). Afterward, all power supplies are turned off, and the chamber is heated to 200°C. Once stabilized, this temperature is maintained for 10 minutes to prepare NiO with a thickness of 20–40 nm. x -V thin film, and use it as a hole transport layer;

[0051] Step 3: Prepare the NiO x The -V thin-film hole transport layer is delivered to the third chamber via a valve. This third chamber is the sputtering deposition chamber for NiO. x Before coating the -V thin-film hole transport layer, the third common chamber is evacuated to a background vacuum of 3×10⁻⁶. -4 Pa, turn on the T3 RF power supply and set its power to 300W, then install the CsPb (1:1) alloy target, then turn on the T4 RF power supply and set its power to 30W, and install the Sn target at the same time. Then turn on the rotation device, adjust the angle between the cathode of the T3 and T4 targets and the vertical line of the pilot line to 80°, and introduce high-purity argon (Ar) as the sputtering gas. Connect the electron cyclotron resonator to high-purity iodine (I2): bromine (Br2) = 2:1 as the reaction gas to fully ionize it and form a high-performance ion source for co-sputtering. After the T3 and T4 sputtering power supplies are turned off, the electron cyclotron resonator is kept on for 3 minutes to stabilize the absorption layer structure. A CsPb I2Br-Sn film with a thickness of 300-500 nm can be prepared and used as a perovskite absorption layer.

[0052] Subsequently, after the sputtering power supply was turned off, in-situ segmented heating was started. First, the temperature was lowered to 50-100°C for 5-10 minutes, and then heated to 100-150°C for 5-15 minutes to stabilize the perovskite absorber layer structure.

[0053] It should be noted that the perovskite absorber layer is a combination of Cs, Sn, Rb, Pb, I, Br, and Cl, with trace amounts of Sn or K doped within it, for example: CsPbI₂Br doped with Sn, CsPbSnCl₄I₂Br, etc. 3-x I x Thin films doped with potassium (K);

[0054] Step 4: The prepared CsPb I2Br-Sn thin film is transported to the fourth chamber through a valve. The fourth chamber is a buffer rotating chamber. The sample holder magnetic rotation device 6 in the fourth chamber is turned on, so that the sample holder rotates 180° in the chamber, so that the CsPb I2Br-Sn thin film is in a parallel position ready to enter the fifth co-sputtering coating chamber. At the same time, the heating is turned on. First, it is heated to 80°C and stabilized for 5 minutes, then heated to 140°C and held for 10 minutes. The sample holder magnetic rotation device 6 includes a magnetic device and a sample holder support wheel.

[0055] Step 5: The rotated substrate is transported to the fifth chamber through a valve. The fifth chamber is the co-sputtering deposition chamber. Before depositing the CsPbI2Br-Sn thin film, the fifth chamber is evacuated to a base vacuum level of 3×10⁻⁶. -4 Pa, simultaneously turn on the T5 RF power supply and set its power to 200W, install the W target, turn on the T6 RF power supply and connect it to the plasma power supply, set its power to 30W, install the Ti target, and fully ionize it. Adjust the cathodes of the T5 and T6 targets to an angle of 85° with the vertical line of the pilot line, then introduce high-purity argon (Ar) as the sputtering gas and O2 as the reaction gas for co-sputtering to prepare WO. X -Ti thin film as an electron transport layer;

[0056] The electron transport layer is TiO2, ZnO, SnO2 or WO X It is doped with trace amounts of Ti, Zn, Sn, Al, or W elements, such as WO3. X Ti-doped thin films and TiO2-doped Zn thin films;

[0057] Step Six: Prepare the WO X-Ti thin film is transported to the sixth chamber through a valve. The sixth chamber is the coating chamber. The radio frequency power supply in the sixth chamber is turned on and its power is set to 100W. At the same time, a target material of T7:SnO2:In2O3=99:1 is installed and sputtering is performed to prepare a SnO2:In2O3 thin film with a thickness of 15-60nm. The film is non-conductive, but its light transmittance is significantly improved compared to a single SnO2 film. The buffer and blocking layer is a SnO2:In2O3 thin film doped with In or Zn.

[0058] Step 7: The prepared SnO2:n2O3 thin film is transported to the seventh chamber through a valve. The seventh chamber is the coating chamber. The radio frequency power supply in the seventh chamber is turned on and its power is set to 50W. At the same time, a T8:Ag:Cu=98:2 alloy target is installed and sputtering is performed to prepare an AgCu alloy thin film with a thickness of about 15-120nm as the top electrode. Here, the top electrode can be a single or alloy thin film of Ag, Au, Cu and Al, such as Ag thin film, AgCu alloy thin film, AuCu alloy thin film.

[0059] Step 8: The prepared AgCu thin film module is transported to the eighth chamber through a valve. The eighth chamber is a buffer chamber. The prepared AgCu thin film module is then sent to the second feed rack 8 to complete the preparation of the perovskite solar cell.

[0060] The perovskite solar cell prepared in this embodiment is: V oc =79.21V, I sc =2.5776A, FF=64.01%, photoelectric conversion efficiency η is 12.4%;

[0061] Each chamber is equipped with valves 7 on both sides, which can be selectively opened and closed according to usage requirements.

[0062] Example 2

[0063] Based on Example 1, please refer to Figures 1-3 As shown, it also includes the following steps:

[0064] Step 11: Place the FTO conductive glass substrate to be processed on the first sample holder 1 into the first chamber, turn on the radio frequency (RF) ion source, set the power to 200W, and the time to 25 minutes to achieve the purpose of cleaning the impurities on the substrate surface.

[0065] Steps 1 and 2: The cleaned substrate is transported to the second chamber through a valve. The second chamber is the sputtering deposition chamber. Before deposition, a vacuum is drawn to a base vacuum level of 2×10⁻⁶. -4The T1 RF power supply and plasma power supply are connected together at the T1 cathode, set to a power of 150W. T1 is used as the Mo target to fully ionize metallic Mo. The T2 RF power supply is 15W, and T2 is used as the Cu target. Simultaneously, the rotation device is activated, and the angle between the T1 and T2 target cathodes and the vertical line of the pilot line is adjusted to 85°. High-purity argon (Ar) is introduced as the sputtering gas, and high-purity oxygen (O2) is introduced as the reactant gas for co-sputtering. Afterward, all power supplies are turned off, and the chamber is heated to 150°C. After stabilization, this temperature is maintained for 15 minutes to allow for sufficient nucleation and crystallization of the film, resulting in a MoO film with a thickness of 15–30 nm. x -Cu thin film as hole transport layer;

[0066] It should be noted that the hole transport layer in this application is NiO. x Or a MoO3 thin film, doped with trace amounts of V, Co, Fe, or Cu, for example: NiO x V-doped, MoO3-doped, Cu-doped, NiO-doped x Fe-doped, MoO3-doped, Co-doped, NiO-doped x Cu-doped and MoO3-doped Fe thin films;

[0067] Step 13: The prepared MoOx-Cu thin film hole transport layer is transported to the third chamber through a valve. The third common chamber is the sputtering deposition chamber. Before deposition, the vacuum level is evacuated to a background vacuum of 2×10⁻⁶. -4 At step 1, turn on the T3 RF power supply and set the power to 200W. Install the CsPbSn (3:1:1) alloy target. Connect the electron cyclotron resonator to the T4 RF power supply and set the power to 10W. Turn on the rotation device and install the K target. Adjust the angle between the cathodes of the T3 and T4 targets and the vertical line of the pilot line to 80°. Introduce high-purity argon (Ar) as the sputtering gas and high-purity iodine (I2):chlorine (Cl2) = 1:2 as the reaction gas to form a high-performance K ion source for co-sputtering. K doping is beneficial to the carrier activity of the perovskite absorber layer. After the T3 and T4 sputtering power supplies are turned off, the electron cyclotron resonator is kept on for 1 minute to stabilize the absorber layer structure. A CsPbSnCl3 target with a thickness of 300–700 nm is prepared. 3-x I x -K thin film as perovskite absorber layer;

[0068] It should be noted that in this application, a perovskite absorber layer is prepared, which is a thin film doped with trace amounts of Sn or K elements in combination with Cs, Sn, Rb, Pb, I, Br, and Cl, for example: CsPbI₂Br doped with Sn, CsPbSnCl₂I₂, etc. 3-x I x K-doped thin films;

[0069] Step 14: Prepare CsPbSnCl₂ 3-x Ix -K thin film is transported to the fourth chamber through a valve. The fourth chamber is a buffer rotating chamber. The magnetic device and sample holder support wheel in the fourth chamber are turned on, so that the sample holder rotates 180° in the chamber and is prepared to enter the fifth co-sputtering coating chamber in a parallel position. At the same time, heating is turned on. First, it is heated to 50°C, stabilized and maintained for 2 minutes, and then heated to 110°C and maintained for 20 minutes.

[0070] Step 15: The rotated substrate is transported to the fifth chamber through a valve. The fifth chamber is the co-sputtering coating chamber. Before coating, the vacuum level is evacuated to a base vacuum of 2×10⁻⁶. -4 At step 1, turn on the T5 RF power supply and set the power to 100W. Install the Al target. Turn on the T6 RF power supply and connect it to the plasma power supply, setting the power to 20W. Install the Zn target and ensure it is fully ionized. Adjust the angle between the cathodes of the T5 and T6 targets and the vertical line of the pilot line to 75°. Introduce high-purity argon (Ar) as the sputtering gas and O2 as the reactant gas for co-sputtering to prepare Al₂O₃. X -Zn thin films serve as electron transport layers;

[0071] Step 16: Prepare Al₂O₃ X - The Zn thin film is delivered to the sixth chamber through a valve. The radio frequency power supply is turned on and connected to the plasma source, which is set to 80W. At the same time, a T7:Sn:Zn = 99.5:0.5 target material is installed. High-purity argon (Ar) is introduced as the sputtering gas and O2 is introduced as the reaction gas for sputtering to prepare SnO2:ZnO thin films with a thickness of 15-60nm. The film is non-conductive, but its light transmittance is significantly improved compared to a single SnO2 film.

[0072] Step 17: The prepared SnO2:ZnO thin film is transported to the seventh chamber through a valve, the radio frequency power supply is turned on and the power is set to 50W. At the same time, the T8:Au:Cu=96:4 alloy target is installed and sputtering is performed to prepare an AuCu alloy thin film with a thickness of about 10-40nm.

[0073] Step 18: The component with the prepared AuCu thin film is transported to the eighth buffer chamber through the valve and sent to the second feeding rack 8 to complete the preparation of the perovskite solar cell;

[0074] In this embodiment, the perovskite solar cell prepared is: V oc =79.25V, I sc =2.62A, FF=65.25%, photoelectric conversion efficiency η is 12.87%.

[0075] Example 3

[0076] Please see Figures 1-4As shown, a magnetron sputtering device for perovskite solar cells is used to perform a method for fabricating perovskite solar cells. It includes a chamber body, which is divided into a first chamber, a second chamber, a third chamber, a fourth chamber, a fifth chamber, a sixth chamber, a seventh chamber, and an eighth chamber by a plurality of valves 7 arranged sequentially. The first chamber is a plasma chamber, the second chamber is a sputtering deposition chamber, the third chamber is a co-sputtering deposition chamber, the fourth chamber is a buffer rotating chamber, the fifth chamber is a sputtering deposition chamber, the sixth chamber is a deposition chamber, the seventh chamber is a deposition chamber, and the eighth chamber is a buffer chamber. The valves 7 between each chamber are selectively openable / closeable valves.

[0077] A first sample holder 1 is provided on the outside of the first chamber. The first sample holder 1 is used to transport the substrate into the first chamber and to send the substrate with the coating completed out of the first chamber. A second feeder 8 is provided on the outside of the eighth chamber. The second feeder 8 is used to transport the substrate into the eighth chamber and to send the substrate with the coating completed out of the eighth buffer chamber.

[0078] Both the first sample holder 1 and the second feeder 2 can support various substrates with a height of ≤50cm*width of 40cm*thickness of 0.3cm;

[0079] The first chamber contains a radio frequency (RF) ion source for cleaning impurities on the substrate surface, improving film adhesion and coating quality. The second chamber contains two RF power supplies, with two planar targets placed opposite each other. The angle between the target cathode and the perpendicular line to the pilot line is adjustable within the range of 70° to 90°. Ni and Ni-type ionizers can be installed. The third chamber contains targets such as O, Mo, MoO3, V, Co, Fe, and Cu; the fourth chamber contains two radio frequency power supplies, one electron cyclotron resonance (ECR) source, and two planar targets placed opposite each other, with the angle between the target cathode and the vertical line of the pilot line adjustable from 70° to 90°; targets such as Cs, Sn, Rb, K, and Pb can be installed. The chamber is coated with an anti-corrosion coating for protection, allowing the introduction of gases such as I, Br, and Cl. The fifth chamber contains a magnetic device and sample holder support wheels, allowing the sample holder to rotate 180° in the fourth buffer rotating chamber and enter the fifth chamber in a parallel position. The fifth chamber contains two radio frequency power supplies, one plasma source, and two planar targets placed opposite each other, with the angle between the target cathode and the vertical line of the pilot line adjustable from 70° to 90°; targets such as Ti, TiO2, Zn, ZnO, Sn, Al, and W can be installed. The sixth chamber contains one planar target, one radio frequency power supply, and one ion source; targets such as Sn and TiO2 can be installed. The seventh chamber contains a planar target and an RF power supply, and can be equipped with metal or alloy targets such as Ag, Au, Cu and Al. The eighth chamber is a transition buffer chamber.

[0080] It should be noted that all target cathodes are the same size. Co-sputtering simply involves loading a rotating shaft behind the cathode, which can form a motion trajectory, allowing the target to rotate and tilt, thus achieving adjustable angle. It can also be converted into a planar target for individual sputtering. The sputtering angle can be adjusted as needed to achieve controllable and adjustable doping amount.

[0081] The first and second chambers share a mechanical pump 2 and a Roots pump 3, while the second chamber has its own molecular pump 4. The third chamber is equipped with its own mechanical pump 2, Roots pump 3, and molecular pump 4. The fourth chamber has its own mechanical pump 2. The fifth, sixth, seventh, and eighth chambers share mechanical pump 2 and Roots pump 3, while the sixth, seventh, and eighth chambers share a molecular pump 4.

[0082] Each chamber is equipped with a reciprocating conveyor for transporting the substrate within the chamber. A reciprocating conveyor is also provided between every two adjacent connected chambers for transporting the substrate between adjacent chambers. This facilitates efficient substrate transfer between chambers, improving production efficiency. The second, third, and fifth chambers are each equipped with a rotation device for substrate rotation, which allows for more uniform coating during the film deposition process, improving the quality and performance stability of the thin film.

[0083] Both the second and fourth chambers are equipped with chamber heaters that can heat up to 500°C, which allows for heating of the corresponding chambers according to actual needs and to meet different process requirements.

[0084] To ensure the smooth implementation of this solution, it is also necessary to understand that all electrical components mentioned in this article are installed in the unused areas of this device and are electrically connected to the external main controller and 220V AC mains power. Furthermore, the main controller can be a conventional known device such as a computer that provides control.

[0085] Example 4

[0086] As a fourth embodiment of the present invention, in specific implementation, compared with embodiments one, two and three, the technical solution of this embodiment is to combine the solutions of embodiments one, two and three and embodiments four.

[0087] The foregoing has provided a detailed description of one embodiment of the present invention, but this description is merely a preferred embodiment and should not be construed as limiting the scope of the invention. All equivalent variations and modifications made within the scope of the claims of this invention should still fall within the patent coverage of this invention.

Claims

1. A method for preparing a perovskite solar cell, characterized by, Comprising the following steps: Step one: the glass substrate to be processed is transported into the first chamber, and the radio frequency ion source is turned on to clean the impurities on the surface of the substrate; Step two: the cleaned conductive glass substrate is transported into the second chamber through the valve, and sputtering film is plated. Before film plating, the chamber is vacuumed to a certain base vacuum degree, the radio frequency power of T1 and T2 is set, and the corresponding target material is installed. By adjusting the included angle between the target material cathode and the middle test line, the sputtering gas and the reaction gas are inputted, and co-sputtering is carried out. Finally, the power is turned off, and the chamber is heated to a certain temperature and kept for a period of time, so as to prepare a hole transport layer. Here, the hole transport layer is an N iO x or MoO3 film doped with a small amount of V, Co, Fe or Cu elements. Step three: the prepared hole transport layer is transported into the third chamber, and co-sputtering is performed. Before sputtering, the chamber is evacuated, and then the radio frequency power of T3 and T4 is set, and the corresponding target material is installed. By adjusting the angle between the target cathode and the middle test line, the sputtering gas and the reaction gas are introduced for co-sputtering to prepare the perovskite absorption layer. Subsequently, after the sputtering power is turned off, the in-situ segmented heating is turned on. First, heat at a low temperature of 50-100℃ for 5-10 minutes, and then heat at a temperature of 100-150℃ for 5-15 minutes. Here, the perovskite absorption layer is a combination of Cs, Sn, Rb, Pb, I, Br and Cl, with a small amount of Sn or K element doped; Step four: the prepared perovskite absorption layer is transported into the fourth chamber, and the substrate is transported into the fifth chamber after rotating adjustment by the sample holder magnetic rotating device (6); Step five: the prepared perovskite absorption layer is transported into a fifth chamber, the substrate is co-sputtered in the fifth chamber, vacuum is first extracted to a certain base vacuum degree, then a radio frequency power source power is set, the position of the target material is adjusted, and co-sputtering is started, a sputtering gas and a reaction gas are used, and an electron transport layer is prepared by a co-sputtering method, and the electron transport layer is TiO2, ZnO, SnO2, or WO X , wherein trace Ti, Zn, Sn, Al, or W elements are doped. Step six: the prepared electron transport layer is transported into the sixth chamber, and sputtering is performed to prepare a buffer barrier layer. Here, the buffer barrier layer is a SnO2:In2O3 thin film, with In or Zn element doped; Step seven: the prepared SnO2:In2O3 thin film is transported into the seventh chamber, and sputtering is performed to prepare an alloy thin film as a top electrode. The specific method for preparing the alloy thin film is as follows: The top electrode is an Ag thin film, an AgCu alloy thin film or an AuCu alloy thin film made of Ag, Au, Cu and Al alone or in combination; The specific method for preparing the AgCu alloy thin film is as follows: the SnO2:In2O3 thin film is transferred to the seventh chamber, the radio frequency power is set to 50W, and the Ag:Cu=98:2 alloy target material is used for sputtering to prepare the AgCu alloy thin film; Step eight: the prepared AgCu alloy thin film is transported into the eighth chamber to complete the preparation of the perovskite solar cell; A perovskite solar cell special magnetron sputtering device for performing the method comprises a chamber body, and the chamber is divided into a first chamber, a second chamber, a third chamber, a fourth chamber, a fifth chamber, a sixth chamber, a seventh chamber and an eighth chamber by a plurality of valves (7) arranged in sequence; The first chamber is provided with a first sample holder (1) on the outside, and the eighth chamber is provided with a second feeding holder (8) on the outside; The first chamber is provided with one radio frequency ion source, the second chamber and the third chamber are each provided with two radio frequency power sources, the third chamber is further provided with one electron cyclotron resonance source, the fourth chamber is provided with a sample holder magnetic rotating device (6), the fifth chamber is provided with two radio frequency power sources and one plasma source, the sixth chamber is provided with one planar target, one radio frequency power source and one ion source, and the seventh chamber is provided with one planar target and one radio frequency power source.

2. The method for preparing a perovskite solar cell according to claim 1, characterized in that, The specific method for preparing the SnO2:In2O3 thin film is as follows: WO X The Ti film is transferred to the sixth chamber, and a radio frequency power supply is set to 100 W, a SnO2:In2O3=99:1 target is used for sputtering, and a 15-60 nm thick SnO2:In2O3 film is formed.

3. The method for preparing a perovskite solar cell according to claim 2, characterized in that, The specific method for cleaning the surface of the substrate is as follows: The glass substrate is transported into the first chamber, the radio frequency ion source in the first chamber is turned on, and the power is set to 300W and the time is set to 20 minutes to clean the impurities on the surface of the substrate.

4. The method for fabricating a perovskite solar cell according to claim 3, characterized in that, The specific method for preparing the hole transport layer is as follows: The second chamber is vacuumized to a background vacuum degree of 3x10 -4 Pa, the radio frequency power of T1 is set to 100W, then T1 is installed as a Ni target, T2 is installed as a V target, the radio frequency power of T2 is set to 10W, the angle between the target cathode and the middle line is adjusted, high-purity argon Ar is introduced into the second chamber as sputtering gas, the plasma power is connected to high-purity oxygen O2 as reaction gas, the plasma is fully dissociated, co-sputtering is carried out, then all the power is turned off, the chamber is heated to 200℃, and after stabilization, it is kept for 10 minutes, so that a 20-40nm-thick NiO x V film is prepared, which is used as a hole transport layer; The specific method for adjusting the included angle between the target cathode and the pilot line is as follows: The self-rotating device in the second chamber is turned on, and the vertical angle between the T1 and T2 target cathodes and the pilot line is adjusted to 75 degrees.

5. The method for fabricating a perovskite solar cell according to claim 4, characterized in that, The specific method for preparing the perovskite absorption layer is as follows: The prepared NiO x The V thin film hole transport layer is transported into the third chamber through a valve, the third chamber is a sputtering chamber, and the NiO x Before the V thin film hole transport layer is coated, the third chamber is vacuumized to a background vacuum degree of 3*10 -4 Pa, the T3 radio frequency power source is turned on and the power thereof is set to 300 W, then the CsPb 1：1 alloy target, the T4 radio frequency power source is turned on and the power thereof is set to 30 W, at the same time, the Sn target is installed, then the self-rotation device is turned on, the included angle between the cathodes of the T3 and T4 targets and the vertical line of the middle test line is adjusted to 80°, high-purity argon Ar is introduced as a sputtering gas, the electron cyclotron resonance source is connected to high-purity iodine gas I2: bromine gas Br2 = 2:1 as a reaction gas, so that the high-performance ion source is fully ionized to perform co-sputtering, after the T3 and T4 sputtering power sources are turned off, the electron cyclotron resonance source is maintained to be turned on for 3 min to stabilize the structure of the absorption layer; then, heating is turned on, first heated to 80℃, maintained for 5 min after stabilization, then heated to 140℃, maintained for 10 min; a CsPbI2Br-Sn thin film with a thickness of 300-500 nm is prepared as a perovskite absorption layer.

6. The method for fabricating a perovskite solar cell according to claim 5, characterized in that, WO X A specific way of using Ti thin films as electron transport layers is: Before coating the CsPb I2Br-Sn film, the fifth chamber is vacuumed to a background vacuum degree of 3x10 -4 Pa, the power of the radio frequency power supply is set to 200 W, the W target is installed, the T6 radio frequency power supply is turned on and connected to the plasma power supply, the power is set to 30 W, the Ti target is installed, and the T5 and T6 target cathodes are adjusted to be perpendicular to the pilot line at an angle of 85°, then high-purity argon Ar is introduced as a sputtering gas, and O2 is introduced as a reaction gas, and co-sputtering is performed to prepare a WO X The Ti film is used as an electron transport layer.

7. The method for fabricating a perovskite solar cell according to claim 1, characterized in that, The first chamber is a plasma chamber, the second chamber is a sputtering chamber, the third chamber is a co-sputtering chamber, the fourth chamber is a buffer rotation chamber, the fifth chamber is a sputtering chamber, the sixth chamber is a coating chamber, the seventh chamber is a coating chamber, and the eighth chamber is a buffer chamber.

8. The method for fabricating a perovskite solar cell according to claim 7, characterized in that, The first chamber and the second chamber are jointly provided with a mechanical pump (2) and a Roots pump (3), the second chamber is provided with a molecular pump (4), the third chamber is provided with a mechanical pump (2), a Roots pump (3) and a molecular pump (4), the fourth chamber is provided with a mechanical pump (2), and the fifth chamber, the sixth chamber, the seventh chamber and the eighth chamber are jointly provided with a mechanical pump (2) and a Roots pump (3), and the sixth chamber, the seventh chamber and the eighth chamber are jointly provided with a molecular pump (4).

9. The method for fabricating a perovskite solar cell according to claim 8, characterized in that, The second chamber and the fourth chamber are provided with chamber heaters, and the first chamber, the second chamber, the third chamber, the fourth chamber, the fifth chamber, the sixth chamber, the seventh chamber and the eighth chamber are provided with reciprocating conveying devices.

Images