Perovskite-silicon-based tandem solar cell and manufacturing method thereof

Abstract

The application discloses a perovskite-silicon-based laminated solar cell and a manufacturing method thereof, and relates to the technical field of laminated solar cells, and is used for obtaining the perovskite-silicon-based laminated solar cell with high open-circuit voltage and high short-circuit current while retaining the texture structure of a bottom cell. The manufacturing method of the perovskite-silicon-based laminated solar cell comprises the following steps: providing a substrate, wherein the substrate comprises a silicon-based bottom cell with a texture structure, a charge recombination layer and a first carrier transport layer which are sequentially stacked; forming a perovskite light absorption layer composed of two perovskite layers, i.e., a first perovskite layer and a second perovskite layer, on the first carrier transport layer with a texture structure; the first perovskite layer is prepared by using a solution method, and the second perovskite layer is prepared by using a vacuum evaporation perovskite skeleton method. The manufacturing method provided by the application is used for manufacturing a laminated solar cell.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of laminated solar technology, and particularly relates to a perovskite-silicon-based laminated solar cell and a manufacturing method thereof. BACKGROUND

[0002] The perovskite-silicon-based laminated solar cell is made of a silicon-based cell as a bottom cell, a perovskite cell as a top cell, and a tunneling composite layer in between.

[0003] In the manufacturing process of the perovskite-silicon-based laminated solar cell, each functional layer of the perovskite cell needs to be uniformly spin-coated on the pyramid-shaped texturing structure of the silicon-based cell. However, the thickness of each functional layer of the perovskite cell is only a few hundred nanometers, which is difficult to be deposited on the micron-level pyramid-shaped texturing structure by the solution spin-coating method. Although polishing the bottom cell to reduce the roughness of the texturing structure makes it possible to prepare the perovskite cell by the solution spin-coating method, the efficiency gain brought by the texturing structure is lost, and the manufacturing cost is greatly increased. Therefore, how to obtain a high-efficiency perovskite-silicon-based laminated solar cell while retaining the texturing structure of the bottom cell is a problem to be solved at present. SUMMARY

[0004] The present application aims to provide a perovskite-silicon-based laminated solar cell and a manufacturing method thereof, which can obtain a perovskite-silicon-based laminated solar cell with high open-circuit voltage and high short-circuit current while retaining the texturing structure of the bottom cell.

[0005] In a first aspect, the present application provides a manufacturing method of a perovskite-silicon-based laminated solar cell, comprising:

[0006] providing a substrate, the substrate comprising a silicon-based substrate cell with a texturing structure, a charge recombination layer, and a first carrier transport layer stacked in sequence;

[0007] forming a perovskite light absorption layer composed of two perovskite layers, i.e., a first perovskite layer and a second perovskite layer, on the first carrier transport layer with the texturing structure. The first perovskite layer is prepared by a solution method. The second perovskite layer is prepared by a vacuum evaporation perovskite skeleton method.

[0008] In the above technical solution, the first perovskite layer and the second perovskite layer formed on the first carrier transport layer with the texturing structure constitute the perovskite light absorption layer, wherein the first perovskite layer is prepared by a solution method, and the second perovskite layer is prepared by a vacuum evaporation perovskite skeleton method. The vacuum evaporation perovskite skeleton method is to first vacuum evaporate a mixture of PbX2 and CsY to form a perovskite skeleton, wherein X and Y are selected from chloride (Cl - ), bromide (Br -one or more of iodide ions (I - ) and thiocyanate ions (SCN - ), the mixture of two can be a mixture of two or more than three materials, preferably a mixture of lead iodide and cesium iodide or a mixture of lead iodide and cesium bromide; then the existing solution coating method such as solution spin coating, blade coating, spraying and the like is used to cover the perovskite skeleton with an organic amine solution to form a perovskite film by reaction. The formed second perovskite layer can conformally cover the pointed top and slope of the textured structure, and the first perovskite layer formed by the solution method can be stacked and partially filled in the bottom of the textured structure. Based on this, the perovskite light absorption layer composed of the above two perovskite layers has the advantages of both solution method and vacuum evaporation method, while avoiding the disadvantages of the two methods; both the good light trapping effect and the antireflection effect of the textured structure are well retained to obtain a high short-circuit current, and the solution components can be conveniently adjusted to obtain the required wide band gap and high open-circuit voltage. As can be seen, compared with the prior art, the manufacturing method of the perovskite-silicon-based stacked solar cell provided by the present application well balances the contradiction between the conformality of the textured structure and the regulation of the perovskite component, greatly widening the process regulation window and the range of component and material selection for the preparation of high-efficiency stacked cells.

[0009] In some possible implementation manners, when the average vertical distance from the lowest end to the highest end of the textured structure of the first carrier transport layer is L, the average thickness of the first perovskite layer prepared by the solution method ranges from greater than 0 to less than or equal to 1 / 2L. At this time, the first perovskite layer prepared by the solution method is stacked at the bottom of the textured structure of the first carrier transport layer, and the thickness is less than or equal to half of the height of the textured structure. Based on this, the formed perovskite absorption layer can maintain good textured characteristics, that is, when the perovskite light absorption layer is irradiated, the textured structure thereof can utilize the light trapping effect and the antireflection effect to improve the photoelectric conversion efficiency. When the thickness of the first perovskite layer prepared by the solution method is greater than half of the height of the textured structure, the textured structure of the formed perovskite light absorption layer has a smaller height, a higher reflectivity to light and a lower photoelectric conversion efficiency.

[0010] In some possible implementation manners, forming the perovskite light absorption layer composed of the first perovskite layer and the second perovskite layer on the first carrier transport layer with the textured structure includes: preparing the first perovskite layer on the first carrier transport layer with the textured structure by the solution method. Then, the second perovskite layer is prepared by the vacuum evaporation perovskite skeleton method.

[0011] In the technical solution, the perovskite light absorption layer can be prepared by a two-step method of solution method followed by vacuum evaporation perovskite skeleton method. Specifically, a first perovskite layer is formed on the first carrier transport layer with a textured structure by the solution method, and a second perovskite layer is formed on the first perovskite layer by the vacuum evaporation perovskite skeleton method. Based on this, the first perovskite layer prepared by the solution method is stacked at the bottom of the textured structure of the first carrier transport layer, and the band gap of the perovskite can be adjusted by changing the composition of the perovskite solution. The second perovskite layer prepared by the vacuum evaporation perovskite skeleton method conformally covers the first perovskite layer and the un-filled textured structure without changing the textured structure, thereby retaining the textured structure to obtain good light trapping effect and anti-reflection properties, and ensuring that the textured structure is covered to avoid short circuit caused by direct contact of the electrode with the textured structure. The stacked cell prepared by the method has the advantages of existing stacked cell solutions, avoids the shortcomings of existing technologies, and well balances the contradiction between the textured conformality and the solution composition adjustment.

[0012] In some possible implementation manners, forming the perovskite light absorption layer composed of the first perovskite layer and the second perovskite layer on the first carrier transport layer with a textured structure includes: preparing the second perovskite layer on the first carrier transport layer with a textured structure by the vacuum evaporation perovskite skeleton method, and then preparing the first perovskite layer by the solution method.

[0013] In the technical solution, the perovskite light absorption layer can be prepared by a two-step method of solution method followed by vacuum evaporation perovskite skeleton method. Specifically, a first perovskite layer is formed on the first carrier transport layer with a textured structure by the solution method, and a second perovskite layer is formed on the first perovskite layer by the vacuum evaporation perovskite skeleton method. Based on this, the first perovskite layer prepared by the solution method is stacked at the bottom of the textured structure of the first carrier transport layer, and the band gap of the perovskite can be adjusted by changing the composition of the perovskite solution. The second perovskite layer prepared by the vacuum evaporation perovskite skeleton method conformally covers the first perovskite layer and the un-filled textured structure without changing the textured structure, thereby retaining the textured structure to obtain good light trapping effect and anti-reflection properties, and ensuring that the textured structure is covered to avoid short circuit caused by direct contact of the electrode with the textured structure. The stacked cell prepared by the method has the advantages of existing stacked cell solutions, avoids the shortcomings of existing technologies, and well balances the contradiction between the textured conformality and the solution composition adjustment.

[0014] In some possible implementation manners, forming the perovskite light absorption layer composed of the first perovskite layer and the second perovskite layer on the first carrier transport layer with a textured structure includes: preparing the second perovskite layer on the first carrier transport layer with a textured structure by the vacuum evaporation perovskite skeleton method, and then preparing the first perovskite layer by the solution method.

[0015] In the method for preparing the second perovskite layer by the vacuum evaporation perovskite skeleton method first and the solution method for preparing the first perovskite layer, the second perovskite layer can be prepared by vacuum evaporation of the perovskite skeleton first and then by the one-step method for preparing the first perovskite layer and the second perovskite layer. When the solution used in the solution method is coated on the perovskite skeleton, the excess organic amine contained in the solution reacts with the perovskite skeleton to form the second perovskite layer. The formed second perovskite layer conformally covers the textured structure. The first perovskite layer prepared by the solution method is deposited and partially fills the bottom of the textured structure covered with the second perovskite layer, forming the perovskite light-absorbing layer.

[0016] In some possible implementations, the solute of the solution used in the solution method is a mixed perovskite component Cs x FA y MA z PbBr m I n (x+y+z=1,m+n=3),and the solvent is one or more of N,N-dimethylformamide and dimethyl sulfoxide. In the method for preparing the first perovskite layer and the second perovskite layer by vacuum evaporation of the perovskite skeleton first and then by the one-step method, the solution used not only includes the mixed components of lead iodide and formamidinium hydroiodide, methylamine bromide and formamidinium hydrobromide that satisfy the above-mentioned ratio, but also includes an excess of the organic amine component. The excess organic amine component reacts with the perovskite skeleton to form the second perovskite layer that conformally covers the textured structure.

[0017] In some possible implementations, the vacuum evaporation perovskite skeleton method includes vacuum evaporation of the perovskite skeleton first and then reaction of the perovskite skeleton with the organic amine to form the second perovskite layer. The perovskite skeleton is a mixture of two or more than two of PbX2and CsY. X and Y are each one or more selected from Cl - ,Br - ,I - ,SCN - . The mixture is preferably a mixture of lead iodide and cesium iodide or a mixture of lead iodide and cesium bromide. The organic amine is one or more of formamidinium hydroiodide, methylamine bromide and formamidinium hydrobromide. The main component of the perovskite skeleton is preferably a mixture of lead iodide and cesium iodide or a mixture of lead iodide and cesium bromide. During vacuum evaporation of the perovskite skeleton, lead iodide and cesium iodide or lead iodide and cesium bromide can be co-evaporated as needed to adjust the band gap size of the perovskite to obtain a high open-circuit voltage.

[0018] In some possible implementation manners, the concentration of the solution used in the solution method is 0.2 mol / L to 3 mol / L. In the process of first vacuum evaporating the perovskite skeleton and then simultaneously preparing the first perovskite layer and the second perovskite layer by using the one-step method, if the concentration of the solution used in the solution method is too small, the solvent in the solution used in the solution method can quickly dissolve the lead iodide in the perovskite skeleton and shake out the lead iodide from the suede structure in the process of coating, which can damage the perovskite skeleton and cannot form a uniform and continuous perovskite thin film. Preferably, when the concentration of the solution used in the solution method is greater than 1 mol / L, the speed of the solvent in dissolving the lead iodide in the perovskite is slow or even cannot dissolve the lead iodide in the lower layer in the process of coating, which ensures the shape retention of the perovskite thin film on the suede structure.

[0019] In some possible implementation manners, the method for vacuum evaporating the perovskite skeleton comprises: spin coating an organic amine solution on the perovskite skeleton. In this method, the rotation speed of the spin coating is 500 rpm to 6000 rpm, and the thickness of the perovskite skeleton ranges from 50 nm to 1000 nm.

[0020] In some possible implementation manners, after the perovskite light-absorbing layer is formed, the method for manufacturing the perovskite-silicon-based stacked solar cell further comprises: sequentially forming a second carrier transport layer, a transparent conductive layer and an electrode on the perovskite light-absorbing layer.

[0021] In the second aspect, the present application further provides a perovskite-silicon-based stacked solar cell, which is manufactured by using the above method for manufacturing the perovskite-silicon-based stacked solar cell.

[0022] The perovskite-silicon-based stacked solar cell provided in the second aspect has the same beneficial effects as the method for manufacturing the perovskite-silicon-based stacked solar cell described in the first aspect or any possible implementation manner of the first aspect, which will not be repeated here.

[0023] In the third aspect, the present application further provides a perovskite-silicon-based stacked solar cell, which comprises a silicon-based substrate cell with a suede structure, a charge recombination layer and a first carrier transport layer which are sequentially stacked, and a perovskite light-absorbing layer covering the first carrier transport layer with a suede structure. The perovskite light-absorbing layer is composed of two perovskite layers, i.e., a first perovskite layer and a second perovskite layer. The first perovskite layer is prepared by using a solution method, and the second perovskite layer is prepared by using a method for vacuum evaporating a perovskite skeleton.

[0024] The perovskite-silicon-based stacked solar cell provided in the third aspect has the same beneficial effects as the method for manufacturing the perovskite-silicon-based stacked solar cell described in the first aspect, which will not be repeated here.

[0025] In some possible implementation manners, the first perovskite layer is distributed at least at the bottom of the valley of the texture structure of the first carrier transport layer, and the average thickness of the first perovskite layer is less than or equal to 1 / 2 of the height of the texture structure. The partial structure of the second perovskite layer is distributed at least at the slope and top of the texture structure, and maintains the same texture shape at the slope and top. The perovskite-silicon-based stacked solar cell formed based on this has good shape retention on one hand, and retains good light trapping and anti-reflection effects of the texture structure to facilitate obtaining a high short-circuit current. On the other hand, the perovskite-silicon-based stacked solar cell is easier to manufacture compared with directly forming a perovskite structure with a good shape, and can also conveniently regulate solution components to obtain a required wide band gap and high open-circuit voltage.

[0026] In some possible implementation manners, the thickness of the first carrier transport layer ranges from 5 nm to 200 nm. The average thickness of the perovskite light absorption layer ranges from 100 nm to 3000 nm.

[0027] In some possible implementation manners, the average thickness of the first perovskite layer ranges from 100 nm to 300 nm, and the thickness of the second perovskite layer ranges from 100 nm to 3000 nm. BRIEF DESCRIPTION OF DRAWINGS

[0028] The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:

[0029] Figure 1 A schematic diagram of a perovskite light absorption layer prepared only by a solution method in the prior art;

[0030] Figure 2 A schematic diagram of a perovskite light absorption layer prepared only by a vacuum evaporation method in the prior art;

[0031] Figure 3 A schematic diagram of a first carrier transport layer with a texture structure provided in an embodiment of the application;

[0032] Figure 4 A schematic diagram of a first perovskite layer prepared by a solution method in an embodiment of the application;

[0033] Figure 5 A schematic diagram of a second perovskite layer prepared by a vacuum evaporation method in an embodiment of the application;

[0034] Figure 6 A schematic diagram of a second perovskite layer prepared by a vacuum evaporation method in an embodiment of the application;

[0035] Figure 7A schematic diagram of a first perovskite layer prepared by a solution method is provided for an embodiment of the present application.

[0036] Figure 8 A structure schematic diagram of a perovskite-silicon-based stacked solar cell is provided for an embodiment of the present application.

[0037] Figure 9 A schematic diagram of a textured structure of a perovskite-silicon-based stacked solar cell is provided for an embodiment of the present application.

[0038] Reference signs:

[0039] 101-n-type crystalline silicon wafer, 102-first passivation layer, 103-second passivation layer, 104-n-type amorphous / microcrystalline silicon layer, 105-p-type amorphous / microcrystalline silicon layer, 106-first transparent conductive layer, 107-charge recombination layer, 1070-n-type doped microcrystalline silicon layer, 1071-p-type doped microcrystalline silicon layer, 108-first carrier transport layer, 109-perovskite light absorption layer, 110-second carrier transport interface layer, 1100-second carrier transport interface layer one, 1101-second carrier transport interface layer two, 111-second carrier transport layer, 112-second transparent conductive layer, 113-electrode, 1090-first perovskite layer, 1091-second perovskite layer. DETAILED DESCRIPTION

[0040] In order to make the technical problems to be solved by the present application, technical solutions and beneficial effects more clearly understood, the present application will be further described in detail below in conjunction with the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and not intended to limit the present application.

[0041] It should be noted that when an element is referred to as being "fixed to" or "set on" another element, it can be directly on the other element or indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or indirectly connected to the other element.

[0042] In addition, the terms "first", "second" are only for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "a plurality of" is two or more, unless otherwise explicitly and specifically limited. The meaning of "several" is one or more, unless otherwise explicitly and specifically limited.

[0043] In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "back", "left", "right" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application.

[0044] Organic-inorganic hybrid perovskite solar cells have been widely concerned as a new type of high-efficiency and low-cost solar cells. In just a few years, the photoelectric conversion efficiency of perovskite solar cells has rapidly increased from 3.8% in 2009 to more than 25%, which is close to the efficiency of commercial silicon-based solar cells. Crystalline silicon solar cells are a high-efficiency crystalline silicon photovoltaic cell technology, and the cell efficiency (26.7%) has approached its theoretical limit efficiency (29.4%). The laminated cell technology is an effective way to break through the efficiency of traditional crystalline silicon photovoltaic cells. As a multi-component cell, the absorption band gap of perovskite solar cells can be adjusted in the range of 1.5-1.8 eV by component formulation. Perovskite is an ideal laminated top cell material. Crystalline silicon-perovskite laminated cells use crystalline silicon cells as bottom cells to absorb 800-1200 nm solar energy, and perovskite cells as top cells to absorb 300-800 nm solar energy, and the two are connected by a charge recombination layer to form a series of cells. The overall open-circuit voltage of the laminated cell is the voltage superposition of the top and bottom cells, and the current of the laminated cell needs good current matching between the top and bottom cells. Crystalline silicon-perovskite laminated cells are expected to achieve a photoelectric conversion efficiency of more than 30%.

[0045] Currently, there are several documents reporting that the conversion efficiency of crystalline silicon-perovskite tandem cell has reached more than 25%. A typical perovskite cell is prepared by a solution spin-coating method to prepare each functional layer in the device. High-efficiency crystalline silicon cells generally use a double-textured light-trapping structure to improve the absorption and utilization of sunlight, thereby improving the conversion efficiency of the cell. The micron-scale pyramid textured light-trapping structure in the crystalline silicon cell is a great challenge for the solution method to prepare the perovskite top cell. The difficulty lies in that the thickness of each functional layer of the perovskite cell is generally a few hundred nanometers, which is difficult to be uniformly and conformally deposited on the micron-scale pyramid textured surface by the solution spin-coating method. The current solution is to polish the crystalline silicon bottom cell to reduce the roughness of the textured surface to make it possible to prepare the perovskite top cell by solution. Although this method can prepare the perovskite top cell and the tandem cell by solution, it sacrifices the efficiency gain of the textured structure and its light-trapping effect, and the polishing process greatly increases the manufacturing cost of the entire cell, which is difficult to reflect the advantages of the efficiency gain of the tandem cell. How to retain the textured structure of the bottom cell and directly prepare the perovskite cell on the textured surface of the bottom cell is the key to achieving high efficiency of the tandem cell. There are currently two technical solutions for preparing a perovskite tandem cell on a textured crystalline silicon bottom cell. As shown in Figure 1 and Figure 2 , one is to conformally evaporate a lead iodide film on the textured surface first, and then spin-coat an organic amine solution to generate perovskite in situ; in this method, lead iodide plays an anchoring role to ensure that perovskite forms a film with the textured surface; the second solution is to prepare a small textured (such as a 2-micron textured) substrate and directly spin-coat a perovskite solution to prepare a perovskite film on the small textured surface by one-step method; one-step spin-coating on a small textured surface requires adjusting the thickness of the perovskite film by solution concentration, rotation speed and other parameters to ensure that the perovskite film can fully cover the pyramid tip of the textured surface without being too thick. Both of the above-mentioned solutions have their limitations. The first solution is difficult to ensure that the organic amine solution can fully react with the lead iodide film because the evaporated lead iodide film is relatively dense and has low reactivity, which makes it difficult to guarantee that the organic amine solution can fully react with the lead iodide film and form large-size perovskite grains when the organic amine solution is spin-coated, and thus it is difficult to obtain a wide-bandgap perovskite top cell and a high open voltage through component regulation. The highest conversion efficiency reported in the literature based on this solution is only 25.4%, which is due to the limitations of component regulation. The second solution can easily regulate components to obtain a wide-bandgap and high open voltage, but the film formed does not have conformality, the lower part fills the valley of the textured surface, and the upper part is a flat film, which loses the anti-reflection characteristics of the textured surface and has a high reflectivity. Because of its low absorption, the current is low. Therefore, it is necessary to develop a method for depositing a perovskite film on a large textured crystalline silicon cell to obtain a tandem cell with high open voltage and high current, so as to obtain a high-efficiency crystalline silicon-perovskite tandem cell.

[0046] To solve the above technical problems, the application provides a method for manufacturing a perovskite-silicon-based stacked solar cell.

[0047] As shown in the drawings, Figures 3 to 8 The application provides a method for manufacturing a perovskite-silicon-based stacked solar cell, which comprises the following steps:

[0048] A substrate is provided, which comprises a silicon-based substrate cell with a textured surface, a charge recombination layer 107, and a first carrier transport layer 108.

[0049] First, a silicon-based cell is provided. Taking an n-type silicon-based substrate cell as an example, the manufacturing method can be as follows.

[0050] An n-type crystalline silicon wafer 101 is provided. In actual application, the n-type crystalline silicon wafer 101 can be a commercial silicon wafer with a resistivity of 1 Ω·cm-10 Ω·cm and a thickness of 50 μm-300 μm.

[0051] The n-type crystalline silicon wafer 101 is subjected to texturing and cleaning processes in sequence to form an n-type crystalline silicon wafer 101 with a textured surface. The n-type crystalline silicon wafer 101, as a light absorption layer of the silicon-based substrate cell, converts photons into photo-generated carriers (electron-hole pairs).

[0052] An intrinsic amorphous silicon passivation layer is deposited on both sides of the n-type crystalline silicon wafer 101 to form a first passivation layer 102 on the front side of the n-type crystalline silicon wafer 101 and a second passivation layer 103 on the back side of the n-type crystalline silicon wafer 101. The first passivation layer 102 and the second passivation layer 103 mainly serve to passivate the dangling bonds on the surface of the n-type crystalline silicon wafer 101.

[0053] In actual application, the intrinsic amorphous silicon passivation layer can be manufactured by using a plasma chemical vapor deposition (PECVD) process, a hot-wire chemical vapor deposition process, or a catalytic chemical vapor deposition process. The thickness of the first passivation layer 102 and the second passivation layer 103 can be 1 nm-20 nm.

[0054] A phosphorus-doped n-type amorphous / microcrystalline silicon layer 104 is deposited on the first passivation layer 102 to form a front-side emission level. In actual application, the n-type amorphous / microcrystalline silicon layer 104 can be manufactured by using a PECVD process, a hot-wire chemical vapor deposition process, or a catalytic chemical vapor deposition process. The thickness of the n-type amorphous / microcrystalline silicon layer 104 can be 1 nm-30 nm.

[0055] A boron-doped p-type amorphous / microcrystalline silicon layer 105 is deposited on the second passivation layer 103 to form a back-side structure. In actual application, the p-type amorphous / microcrystalline silicon layer 105 can be manufactured by using a PECVD process, a hot-wire chemical vapor deposition process, or a catalytic chemical vapor deposition process. The thickness of the p-type amorphous / microcrystalline silicon layer 105 can be 1 nm-30 nm.

[0056] A first transparent conductive layer 106 is formed on the p-type amorphous / microcrystalline silicon layer 105. The first transparent conductive layer 106 mainly functions to collect photo-generated carriers and transmit the photo-generated carriers to the back metal electrode 113. Specifically, the material of the first transparent conductive layer 106 can be one or more of indium tin oxide (ITO), tungsten-doped indium oxide (In2O3:W, abbreviated as IWO), indium zinc oxide (IZO), titanium-doped indium oxide (ITiO), and the like, and is not limited thereto.

[0057] In practical applications, the first transparent conductive layer 106 can be made by a magnetron sputtering process. The thickness of the first transparent conductive layer 106 can be 30 nm-120 nm.

[0058] The above process steps form a silicon-based substrate cell. Since the crystalline silicon substrate has a textured structure, the first passivation layer 102, the second passivation layer 103, the n-type amorphous / microcrystalline silicon layer 104, the p-type amorphous / microcrystalline silicon layer 105, and the first transparent conductive layer 106 each have a textured structure.

[0059] A charge recombination layer 107 is deposited on the n-type amorphous / microcrystalline silicon layer 104 to achieve tunneling recombination and collection of photo-generated carriers. The charge recombination layer 107 can be a transparent metal oxide charge recombination layer 107 made of tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), titanium-doped indium oxide (ITIO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), etc. In practical applications, the charge recombination layer 107 can be made by a magnetron sputtering process.

[0060] Of course, the charge recombination layer 107 can also be a heavily doped silicon charge recombination layer 107 opposite to the pn junction of the bottom cell. For example, the charge recombination layer 107 mainly consists of an n-type doped microcrystalline silicon layer 1070 and a p-type doped microcrystalline silicon layer 1071, wherein the p-type doped microcrystalline silicon layer 1071 is close to the perovskite cell described below, and the n-type doped microcrystalline silicon layer 1070 is close to the silicon-based substrate cell. Specifically, the n-type doped microcrystalline silicon layer 1070 can be a phosphorus-doped microcrystalline silicon layer, and the p-type doped microcrystalline silicon layer 1071 can be a boron-doped microcrystalline silicon layer. In practical applications, the charge recombination layer 107 can be made by a PECVD, hot-wire chemical vapor deposition, catalytic chemical vapor deposition, etc. The thickness of the n-type doped microcrystalline silicon layer 1070 and the p-type doped microcrystalline silicon layer 1071 can be 1 nm-30 nm.

[0061] Forming a perovskite cell on the charge recombination layer 107 specifically includes the following steps:

[0062] A first carrier transport layer 108 is formed on the charge recombination layer 107 to realize the vertical transport of photo-generated carriers. The material of the first carrier transport layer 108 can be poly[ bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 2,2',7,7'-tetrakis-(dimethoxyphenylamino)-spirobifluorene (Spiro-OMeTAD), 2,2',7,7'-tetrakis(di-p-tolylamino)spiro-9,9'-bifluorene (Spiro-TTB), or nickel oxide (NiO), and is not limited thereto.

[0063] In practical applications, the first carrier transport layer 108 can be made by magnetron sputtering, laser pulse deposition, thermal evaporation plating, chemical vapor deposition, solution coating, gel-sol, or nanoparticle synthesis by hydrothermal method. The thickness of the first carrier transport layer 108 can range from 5 nm to 200 nm.

[0064] A perovskite light absorption layer 109 is formed on the first carrier transport layer 108. The composition of the perovskite light absorption layer 109 is a combination of one or more perovskite structure materials. The chemical formula of the perovskite material can be ABX3, where A is one or more of CH3NH3 cations, C4H9NH3 cations, NH2=CHNH2 cations, Cs cations; B is a combination of one or both of Pb 2+ , Sn 2+ ; and X is one or more of I - , Cl - , Br - .

[0065] As shown in FIG. 1, the perovskite light absorption layer 109 is made by the following steps: Figures 3 to 7

[0066] The perovskite light absorption layer 109 is formed on the first carrier transport layer 108 with a rough structure and is composed of two perovskite layers, a first perovskite layer 1090 and a second perovskite layer 1091. The first perovskite layer 1090 is prepared by a solution method. The second perovskite layer 1091 is prepared by a vacuum evaporation perovskite skeleton method.

[0067] At this time, the first perovskite layer 1090 and the second perovskite layer 1091 formed on the first carrier transport layer 108 with a rough structure by a two-step method constitute the perovskite light absorption layer 109, wherein the first perovskite layer 1090 is prepared by a solution method, and the second perovskite layer 1091 is prepared by a vacuum evaporation perovskite skeleton method. The vacuum evaporation perovskite skeleton method is to first vacuum evaporate a mixture of PbX2 and CsY to form a perovskite skeleton, where X and Y are respectively selected from chloride ions (Cl - ), bromide ions (Br - ), and iodide ions (I​- ) and thiocyanate ions (SCN - ) and the mixture of two can be a mixture of two or more materials, preferably a mixture of lead iodide and cesium iodide or a mixture of lead iodide and cesium bromide; then an organic amine solution is coated on the perovskite skeleton by using existing solution coating methods such as solution spin coating, blade coating, spraying, etc., to form a perovskite film by reaction. The second perovskite layer 1091 formed can conformally cover the pointed top and slope of the textured structure, and the first perovskite layer 1090 formed by the solution method can be stacked and partially filled in the bottom of the textured structure. Based on this, the perovskite light absorption layer 109 composed of the above two perovskite layers has the advantages of both the solution method and the vacuum evaporation perovskite skeleton method, while avoiding the disadvantages of the two methods; it not only retains the good light trapping effect and antireflection effect of the textured structure to obtain a high short-circuit current, but also can conveniently adjust the solution components to obtain the required wide band gap and high open-circuit voltage. As can be seen, compared with the prior art, the perovskite-silicon-based stacked solar cell manufacturing method provided by the present application well balances the contradiction between the conformality of the textured structure and the regulation of the perovskite component, greatly widening the process regulation window and the range of component and material selection for the preparation of high-efficiency stacked cells.

[0068] In addition, when the average vertical distance of the textured structure from the lowest end to the highest end of the first carrier transport layer 108 is L, the average thickness of the first perovskite layer 1090 prepared by the solution method is greater than 0 and less than or equal to 1 / 2L. At this time, the first perovskite layer 1090 prepared by the solution method is stacked at the bottom of the textured structure of the first carrier transport layer 108, and the thickness is less than or equal to half the height of the textured structure. Based on this, the formed perovskite light absorption layer 109 can maintain good textured characteristics, i.e., when the perovskite light absorption layer 109 is illuminated, the textured structure thereof can use light trapping effect and antireflection effect to improve photoelectric conversion efficiency. When the thickness of the first perovskite layer 1090 prepared by the solution method is greater than half the height of the textured structure, the textured structure of the formed perovskite light absorption layer 109 has a smaller height, a higher reflectivity to light, and a lower photoelectric conversion efficiency. The thickness of the first perovskite layer 1090 prepared by the solution method is defined as the height of the solution deposited on the textured structure from the contact point of the textured structure to the highest point of the solution stacking in the vertical direction. Therefore, the average thickness of the above-mentioned first perovskite layer 1090 is the average value of the aforementioned height.

[0069] As Figure 3 , Figure 4 and Figure 5As shown, as a possible implementation, the perovskite light absorption layer 109 can be prepared by a two-step method of solution method first and vacuum evaporation perovskite skeleton method later. Specifically, forming the perovskite light absorption layer 109 composed of two perovskite layers of the first perovskite layer 1090 and the second perovskite layer 1091 on the first carrier transport layer 108 with the textured structure includes: preparing the first perovskite layer 1090 on the first carrier transport layer 108 with the textured structure by the solution method. Then, preparing the second perovskite layer 1091 by the vacuum evaporation perovskite skeleton method. Based on this, the first perovskite layer 1090 is formed on the first carrier transport layer 108 with the textured structure by the solution method first, and then the second perovskite layer 1091 is formed on the first perovskite layer 1090 by the vacuum evaporation perovskite skeleton method. Based on this, the first perovskite layer 1090 prepared by the solution method is stacked at the bottom of the textured structure possessed by the first carrier transport layer 108, and the band gap of the perovskite can be regulated by changing the composition of the perovskite solution; the second perovskite layer 1091 prepared by the vacuum evaporation perovskite skeleton method conformally covers the first perovskite layer 1090 and the textured structure that is not filled up, thereby retaining the textured structure to obtain good light trapping effect and anti-reflection properties, while ensuring that the textured structure is covered to avoid short circuit caused by the direct contact of the electrode 113 with the textured structure. The stack cell prepared by this method has the advantages of the existing stack cell scheme, avoids the shortcomings in the prior art, and well balances the contradiction between the textured conformality and the solution composition regulation.

[0070] Figure 9 A schematic diagram of the textured structure of the perovskite-silicon-based stack solar cell provided by the embodiment of the application is shown. Figure 9 As shown, on the pyramid-shaped structure possessed by the textured structure, the second perovskite layer 1091 prepared by the vacuum evaporation perovskite skeleton method is in a stepped shape.

[0071] As shown, Figure 3 , Figure 6 and Figure 7As shown, as some possible implementations, the perovskite light absorption layer 109 can be prepared by a two-step method of first vacuum evaporation perovskite skeleton method and then solution method. Specifically, forming the perovskite light absorption layer 109 composed of the first perovskite layer 1090 and the second perovskite layer 1091 on the first carrier transport layer 108 with a textured structure includes: preparing the second perovskite layer 1091 on the first carrier transport layer 108 with a textured structure by vacuum evaporation perovskite skeleton method. Then, the first perovskite layer 1090 is prepared by solution method. Based on this, the second perovskite layer 1091 is first formed on the first carrier transport layer 108 with a textured structure by vacuum evaporation perovskite skeleton method, and then the first perovskite layer 1090 is formed on the second perovskite layer 1091 by solution method. Based on this, the second perovskite layer 1091 prepared by vacuum evaporation perovskite skeleton method conformally adheres to the textured structure of the first carrier transport layer 108, retains the textured structure to obtain good light trapping effect and anti-reflection characteristics; the first perovskite layer 1090 prepared by solution method is deposited at the bottom of the textured structure, which is conducive to obtaining high open-circuit voltage.

[0072] As some possible implementations, in the method of first preparing the second perovskite layer 1091 by vacuum evaporation perovskite skeleton method and then preparing the first perovskite layer 1090 by solution method, the first perovskite layer 1090 and the second perovskite layer 1091 can also be prepared simultaneously by one-step method after vacuum evaporation perovskite skeleton. Specifically, forming the perovskite light absorption layer 109 composed of the first perovskite layer 1090 and the second perovskite layer 1091 on the first carrier transport layer 108 with a textured structure includes: evaporating a perovskite skeleton on the first carrier transport layer 108 with a textured structure by vacuum evaporation method, and then preparing the first perovskite layer 1090 by solution method. The solution used in the solution method contains excess organic amine. During the formation of the first perovskite layer 1090, the materials in the perovskite skeleton react with the organic amine to form the second perovskite layer 1091. Based on this, when the solution used in the solution method is coated on the perovskite skeleton, the excess organic amine contained in the solution will react with the perovskite skeleton to form the second perovskite layer 1091. The generated second perovskite layer 1091 conformally covers the textured structure. The first perovskite layer 1090 prepared by solution method is deposited and partially filled at the bottom of the textured structure covered with the second perovskite layer 1091, forming the perovskite light absorption layer 109.

[0073] In some examples, the solute of the solution used in the solution method is a mixed perovskite component Cs x FA y MA z PbBr m I n(x+y+z = 1, m+n = 3), and the solvent is one or more of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). In the method of vacuum evaporating the perovskite skeleton first and then simultaneously preparing the first perovskite layer 1090 and the second perovskite layer 1091 in one step, the solution used not only includes the mixed components of lead iodide and formamidinium hydroiodide, methylamine bromide, and formamidinium hydrobromide that satisfy the above-mentioned ratio, but also includes an organic amine component that exceeds the aforementioned stoichiometric ratio. The excess organic amine component reacts with the perovskite skeleton to form the second perovskite layer 1091 that conformally covers the textured structure.

[0074] In some examples, the method of vacuum evaporating the perovskite skeleton includes: vacuum evaporating to form the perovskite skeleton first, and then the perovskite skeleton reacts with the organic amine to form the second perovskite layer 1091. The perovskite skeleton is a mixture formed by two or more than three of PbX2and CsY. X and Y are respectively one or more of chloride ions (Cl - ), bromide ions (Br - ), iodide ions (I - ), and thiocyanate ions (SCN - ). The mixture is preferably a mixture of lead iodide and cesium iodide or a mixture of lead iodide and cesium bromide. The organic amine is one or more of formamidinium hydroiodide, methylamine bromide, and formamidinium hydrobromide. The main component of the perovskite skeleton is preferably a mixture of lead iodide (PbI2) and cesium iodide (CsI) or a mixture of lead iodide (PbI2) and cesium bromide (CsBr). When vacuum evaporating the perovskite skeleton, lead iodide and cesium iodide or lead iodide and cesium bromide can be co-vacuum evaporated as needed to adjust the band gap size of the perovskite to obtain a high open-circuit voltage.

[0075] In practical applications, the thickness of the perovskite skeleton ranges from 50 nm to 1000 nm.

[0076] In practical applications, after the organic amine solution is coated on the perovskite skeleton, annealing and drying treatment can be performed at a temperature of 100°C to 200°C for 5 min to 30 min to form the second perovskite layer 1091. When the perovskite skeleton is a mixture of lead iodide (PbI2) and cesium bromide (CsBr), the evaporation rate of lead iodide during vacuum evaporation can be the evaporation rate of cesium bromide can be When the organic amine solution is a mixed solution of formamidinium hydroiodide (FAI) and formamidinium hydrobromide (FABr), the solvent can be selected from ethanol or isopropanol.

[0077] In some examples, the concentration of the solution used in the solution method is 0.2 mol / L to 3 mol / L. In the process of first vacuum evaporating the perovskite skeleton and then simultaneously preparing the first perovskite layer 1090 and the second perovskite layer 1091 by using the one-step method, if the concentration of the solution used in the solution method is too small, the solvent in the solution used in the solution method can quickly dissolve the lead iodide in the perovskite skeleton and shake out the lead iodide from the suede structure in the process of coating, causing damage to the perovskite skeleton and failing to form a uniform and continuous perovskite film. Preferably, when the concentration of the solution used in the solution method is greater than 1 mol / L, the speed of the solvent dissolving the lead iodide in the perovskite is slow or even not fast enough to dissolve the lead iodide in the lower layer, ensuring the shape retention of the perovskite film on the suede structure. In the method of first vacuum evaporating the perovskite skeleton and then simultaneously preparing the first perovskite layer 1090 and the second perovskite layer 1091 by using the one-step method, the concentration of the solution used is 0.1 mol / L to 3 mol / L.

[0078] In practical applications, the solution used in the solution method can be a N,N-dimethylformamide (DMF) / dimethyl sulfoxide (DMSO) (4:1) solution of Cs 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4 In the process of preparing the first perovskite layer 1090 by using the solution method, after the solution is coated on the first carrier transport layer 108 with a suede structure by using the solution method, the solution can be first surface-dried by using a reverse solvent or a wind knife blowing method, and then annealing and drying treatment is performed at a temperature of 70°C to 190°C for 5 min to 60 min to form the first perovskite layer 1090. The average thickness of the first perovskite layer 1090 ranges from 100 nm to 300 nm.

[0079] In practical applications, in the method of first vacuum evaporating the perovskite skeleton and then simultaneously preparing the first perovskite layer 1090 and the second perovskite layer 1091 by using the one-step method, when the perovskite skeleton is a mixture of lead iodide (PbI2) and cesium bromide (CsBr), the solution used in the solution method can be a N,N-dimethylformamide (DMF) / dimethyl sulfoxide (DMSO) (4:1) solution of perovskite components (Cs 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4An excess of formamidine hydroiodate (FAI) and formamidine hydrobromide (FABr) in a DMF / DMSO (4:1) solution is added, wherein the concentrations of FAI and FABr can both range from 0.1 mol / L to 3 mol / L. In the process of preparing the second perovskite layer 1091 using the vacuum evaporation perovskite framework method, after spin-coating the solution onto the perovskite framework, it can be extracted with an anti-solvent (such as anisole), and then annealed at a temperature of 100℃ to 200℃ for 5 min to 30 min to finally form the perovskite light-absorbing layer 109.

[0080] In some examples, the vacuum evaporation perovskite framework method includes spin-coating an organic amine solution onto the perovskite framework. The spin-coating speed is 500 rpm to 6000 rpm, and the thickness of the perovskite framework ranges from 50 nm to 1000 nm.

[0081] In practical applications, the thickness of the second perovskite layer 1091 ranges from 100 nm to 3000 nm. Since the perovskite light-absorbing layer 109 consists of a first perovskite layer 1090 prepared by a solution method and a second perovskite layer 1091 prepared by a vacuum evaporation perovskite framework method, the thickness of the perovskite light-absorbing layer 109 is defined as the distance from the contact point above the textured surface of the first carrier transport layer 108 to the highest point covered by the perovskite light-absorbing layer 109 in the vertical direction. The average thickness of the perovskite light-absorbing layer 109 ranges from 100 nm to 3000 nm.

[0082] like Figure 8 As shown, a second carrier transport layer 111 is formed on the perovskite light-absorbing layer 109 to achieve longitudinal transport of photogenerated carriers. The material of the second carrier transport layer 111 can be C 60 One or more of [6,6]-phenyl-C61-butyrate isomethyl ester (PCBM), tin dioxide (SnO2), and titanium dioxide (TiO2), and not limited thereto.

[0083] In practical applications, a layer of LiF and C can be first prepared on the perovskite light-absorbing layer 109 using a vacuum evaporation process. 60 A thin film layer or PCBM thin film layer serves as the second carrier transport interface layer 110. Then, a second carrier transport layer 111 made of SnO2 or TiO2 is prepared using atomic layer deposition (ALD), chemical vapor deposition, physical vapor deposition, solution coating, or other methods. The thickness of the second carrier transport layer 111 can be 1 nm to 30 nm. It is understood that in practical applications, the second carrier transport interface layer 110 can be omitted.

[0084] When the second carrier transport interface layer 110 includes a second carrier transport interface layer one 1100 and a second carrier transport interface layer two 1101, the second carrier transport interface layer one 1100 can be LiF vacuum evaporated, and the second carrier transport interface layer two 1101 can be C 60 , the thickness of LiF ranges from 0.1 nm to 10 nm, and the thickness of C 60 ranges from 1 nm to 20 nm.

[0085] As shown in FIG. 1, a second transparent conductive layer 112 is formed on the second carrier transport layer 111 to achieve the purpose of horizontal transportation of electrons to the electrode 113 and reduction of optical reflection. The thickness of the second transparent conductive layer 112 ranges from 30 nm to 200 nm. The material and preparation method of the second transparent conductive layer 112 can refer to those of the first transparent conductive layer 106, which will not be described here. Figure 8 An electrode 113 is formed on the first transparent conductive layer 106 and the second transparent conductive layer 112 to collect current. In practical applications, the electrode 113 can be made into fine grid lines and main grid lines by screen printing or mask evaporation. The material of the electrode 113 can be a metal with good conductivity, such as silver, copper, aluminum, etc. The thickness of the electrode 113 ranges from 100 nm to 500 nm.

[0086] The manufacturing method of the perovskite-silicon-based stacked solar cell described in the embodiments of the present application is not limited to N-type silicon wafers, and is also applicable to P-type crystalline silicon cells, TOPCON cells, polycrystalline silicon cells, and cast ingot monocrystalline silicon cells, etc. perovskite stacked cells integrated with perovskite cells; it is also applicable to other types of perovskite and stacked cells, including copper indium gallium selenide-perovskite stacked cells, perovskite-perovskite stacked cells, gallium arsenide-perovskite stacked cells, organic photovoltaic-perovskite stacked cells, etc., and has good versatility and compatibility. In the above manufacturing method of the perovskite-silicon-based stacked solar cell, the first carrier is a hole, and the second carrier is an electron, so the prepared first carrier transport layer 108 is a hole transport layer, and the second carrier transport layer 111 is an electron transport layer. The manufacturing method of the perovskite-silicon-based stacked solar cell provided in the embodiments of the present application is not only limited to the reverse perovskite top cell structure with a hole transport layer as the substrate, but is also applicable to the formal perovskite top cell structure with an electron transport layer as the substrate, i.e. the cell structure from bottom to top can be a textured silicon-based cell, a tunnel junction or a metal oxide composite layer, an electron transport layer, a first perovskite layer and a second perovskite layer, a hole transport layer, a buffer layer, a metal oxide transparent electrode, and an electrode.

[0087] As shown in FIG. 1, a second transparent conductive layer 112 is formed on the second carrier transport layer 111 to achieve the purpose of horizontal transportation of electrons to the electrode 113 and reduction of optical reflection. The thickness of the second transparent conductive layer 112 ranges from 30 nm to 200 nm. The material and preparation method of the second transparent conductive layer 112 can refer to those of the first transparent conductive layer 106, which will not be described here.

[0088] Figure 8 ​As shown, the embodiment of the present application also provides a perovskite-silicon-based stacked solar cell. The perovskite-silicon-based stacked solar cell is obtained by using the above-mentioned method for manufacturing a perovskite-silicon-based stacked solar cell.

[0089] The perovskite-silicon-based stacked solar cell provided by the embodiment of the present application has the same beneficial effects as the method for manufacturing a perovskite-silicon-based stacked solar cell.

[0090] The embodiment of the present application also provides a perovskite-silicon-based stacked solar cell, which comprises a silicon-based substrate cell with a textured structure, a charge recombination layer and a first carrier transport layer which are sequentially stacked, and a perovskite light absorption layer covering the first carrier transport layer with a textured structure. The perovskite light absorption layer is composed of two perovskite layers, i.e., a first perovskite layer and a second perovskite layer. The first perovskite layer is prepared by using a solution method, and the second perovskite layer is prepared by using a vacuum evaporation perovskite skeleton method.

[0091] As some possible implementation manners, the first perovskite layer is distributed at least in the valley bottom of the textured structure of the first carrier transport layer, and the average thickness of the first perovskite layer is less than or equal to 1 / 2 of the height of the textured structure. Part of the structure of the second perovskite layer is distributed at least in the slope and top of the textured structure, and maintains the same textured shape on the slope and top. The perovskite-silicon-based stacked solar cell formed based on this has good shape retention on the one hand, and retains the good light trapping effect and anti-reflection effect of the textured structure so as to obtain a high short-circuit current on the other hand. On the other hand, the manufacturing of this perovskite-silicon-based stacked solar cell is easier to realize compared with directly forming a conformal perovskite structure, and the solution composition can be conveniently regulated to obtain a required wide band gap and high open-circuit voltage.

[0092] In addition, a layer distributed in the valley bottom of the textured structure of the first carrier transport layer can be named as the second perovskite layer, and a layer distributed in the slope and top of the textured structure can be named as the first perovskite layer.

[0093] As some possible implementation manners, the thickness of the first carrier transport layer ranges from 5 nm to 200 nm. The thickness of the perovskite light absorption layer ranges from 100 nm to 3000 nm. The thickness of the second carrier transport layer ranges from 1 nm to 30 nm.

[0094] As some possible implementation manners, the thickness of the first perovskite layer ranges from 100 nm to 300 nm, and the thickness of the second perovskite layer ranges from 100 nm to 3000 nm.

[0095] In order to verify the performance of the perovskite-silicon-based stacked solar cell prepared by the method for manufacturing the perovskite-silicon-based stacked solar cell provided in the embodiments of the present application, the following is described in the manner of comparing the embodiments with the comparative examples.

[0096] Embodiment one

[0097] The method for manufacturing the perovskite-n-type silicon-based stacked solar cell provided in the embodiments of the present application is specifically described as follows:

[0098] In the first step, a commercial n-type silicon wafer with a resistivity of 3 Ω·cm, a thickness of 180 μm and a texturing size of 4 μm is provided. The silicon wafer is subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a texturing surface.

[0099] In the second step, an intrinsic amorphous silicon passivation layer (5 nm in thickness) is deposited on both sides of the n-type monocrystalline silicon substrate by using a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0100] In the third step, an n-type amorphous silicon layer (10 nm in thickness) doped with phosphorus (doping concentration 10 20 cm -3 ) is deposited on the first passivation layer by using a PECVD device to form a front surface emitter.

[0101] In the fourth step, a p-type amorphous silicon layer (10 nm in thickness) doped with boron (doping concentration 10 19 cm -3 ) is deposited on the second passivation layer by using a PECVD device to form a back surface structure.

[0102] In the fifth step, a first transparent conductive layer (100 nm in thickness) made of ITO is prepared on the p-type amorphous silicon layer by using a magnetron sputtering process.

[0103] In the sixth step, an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer are sequentially deposited on the n-type amorphous silicon layer by using a PECVD device to form a tunneling recombination layer (8 nm in thickness).

[0104] In the seventh step, a hole transport layer (15 nm in thickness) made of spiro-TTB is prepared on the tunneling recombination layer by using a vacuum evaporation process, and the evaporation rate is

[0105] In the eighth step, a perovskite component (Cs 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4A DMF / DMSO (4:1) solution of FAI and FABr with a molar ratio of 3:1 was prepared, and 80 μL of the solution was spin-coated on the first perovskite layer at a rotation speed of 2000 rpm and then treated with butyl acetate extraction, followed by annealing at 100℃ for 20 min to form a second perovskite layer (average thickness 550 nm).

[0106] In the ninth step, a vacuum evaporation process was used to form a lead iodide and cesium bromide layer on the first perovskite layer, wherein the cesium bromide (CsBr) rate was 0.1 nm / s. The lead iodide (PbI2) rate was 0.1 nm / s. The total thickness was 400 nm.

[0107] A FAI and FABr mixed solution was prepared, and the molar concentration ratio of FAI and FABr was 3:1, and the solvent was ethanol or isopropanol. 80 μL of the FAI and FABr mixed solution was spin-coated on the lead iodide and cesium bromide layer and reacted to form a second perovskite layer (thickness 550 nm).

[0108] The second perovskite layer was annealed at a temperature of 150℃ for 20 min to form a perovskite light absorption layer (average thickness 550 nm).

[0109] In the tenth step, a vacuum evaporation process was used to sequentially prepare a LiF thin film layer (thickness 1 nm) and a C 60 The thin film layer (thickness 10 nm) served as an electron transport interface layer (thickness 11 nm).

[0110] In the eleventh step, an atomic deposition process (ALD) was used to prepare an electron transport layer (thickness 10 nm) of SnO2 material.

[0111] In the twelfth step, a magnetron sputtering process was used to form a second transparent conductive layer (thickness 100 nm) of ITO material on the electron transport layer.

[0112] In the thirteenth step, a screen printing process was used to form a silver electrode on the first transparent conductive layer and the second transparent conductive layer.

[0113] Example Two

[0114] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiments of the present application is as follows:

[0115] In the first step, a commercial n-type silicon wafer with a resistivity of 3 Ω·cm, a thickness of 180 μm, and a texturing size of 4 μm was provided. The silicon wafer was subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a textured surface.

[0116] In the second step, an intrinsic amorphous silicon passivation layer (thickness 5 nm) was deposited on both sides of the n-type monocrystalline silicon substrate using a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0117] Thirdly, a phosphorus-doped (doping concentration 10 20 cm -3 ) n-type amorphous silicon layer (thickness 10 nm) is deposited on the first passivation layer by a PECVD device to form a front emitter.

[0118] Fourthly, a boron-doped (doping concentration 10 19 cm -3 ) p-type amorphous silicon layer (thickness 10 nm) is deposited on the second passivation layer by a PECVD device to form a back structure.

[0119] Fifthly, a first transparent conductive layer (thickness 100 nm) of ITO material is prepared on the p-type amorphous silicon layer by a magnetron sputtering process.

[0120] Sixthly, an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer are sequentially deposited on the n-type amorphous silicon layer by a PECVD device to form a tunneling recombination layer (thickness 8 nm).

[0121] Seventhly, a hole transport layer (thickness 15 nm) of spiro-TTB material is prepared on the tunneling recombination layer by a vacuum evaporation process, with an evaporation rate of

[0122] Eighthly, a DMF / DMSO (4:1) solution of perovskite components (Cs 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4 ) with a concentration of 0.2 mol / L is spin-coated on the hole transport layer with a textured structure at a rotation speed of 500 rpm, and then treated with anisole extraction, followed by annealing at 70°C for 60 min to form a first perovskite layer (average thickness 100 nm).

[0123] Ninthly, lead iodide and cesium bromide are formed on the first perovskite layer by a vacuum evaporation process, with a cesium bromide (CsBr) rate of a lead iodide (PbI2) rate of and a total thickness of 50 nm.

[0124] An FAI and FABr mixed solution is prepared, with a molar concentration ratio of FAI to FABr being 3:1, and a solvent being ethanol or isopropanol. 70 μL of the FAI and FABr mixed solution is spin-coated on the lead iodide and cesium bromide layer to react and form a second perovskite layer (thickness 100 nm).

[0125] The second perovskite layer is annealed at a temperature of 100°C for 30 min to form a perovskite light absorption layer (average thickness 100 nm).

[0126] The tenth step is to prepare a LiF thin film layer (1 nm in thickness) and a C 60 thin film layer (10 nm in thickness) as an electron transport interface layer (11 nm in thickness) by using a vacuum evaporation process.

[0127] The eleventh step is to prepare an electron transport layer (10 nm in thickness) made of SnO2 by using an atomic deposition process (ALD).

[0128] The twelfth step is to form a second transparent conductive layer (100 nm in thickness) made of ITO on the electron transport layer by using a magnetron sputtering process.

[0129] The thirteenth step is to form a silver electrode on the first transparent conductive layer and the second transparent conductive layer by using a screen printing process.

[0130] Example Three

[0131] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiment of the present application is specifically described as follows:

[0132] The first step is to provide a commercial n-type silicon wafer with a resistivity of 3 Ω.cm, a thickness of 180 μm, and a texturing size of 4 μm. The silicon wafer is subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a texturing surface.

[0133] The second step is to deposit intrinsic amorphous silicon passivation layers (5 nm in thickness) on both sides of the n-type monocrystalline silicon substrate by using a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0134] The third step is to deposit an n-type amorphous silicon layer (10 nm in thickness) doped with phosphorus (10 20 cm -3 ) on the first passivation layer by using a PECVD device to form a front emitter.

[0135] The fourth step is to deposit a p-type amorphous silicon layer (10 nm in thickness) doped with boron (10 19 cm -3 ) on the second passivation layer by using a PECVD device to form a back field structure.

[0136] The fifth step is to prepare a first transparent conductive layer (100 nm in thickness) made of ITO on the p-type amorphous silicon layer by using a magnetron sputtering process.

[0137] The sixth step is to deposit an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer on the n-type amorphous silicon layer in sequence by using a PECVD device to form a tunneling recombination layer (8 nm in thickness).

[0138] In the seventh step, a hole transport layer (15 nm thick) of spiro-TTB is prepared on the tunneling composite layer by vacuum evaporation at an evaporation rate of 0.1 A / s.

[0139] In the eighth step, a DMF / DMSO (4:1) solution of perovskite components (CsFAI3, 3 mol / L) is spin-coated on the hole transport layer with a textured structure at a rotation speed of 6000 rpm, and then extracted with anisole, followed by annealing at 190°C for 5 min to form a first perovskite layer (300 nm thick on average). 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4

[0140] In the ninth step, lead iodide and cesium bromide are formed on the first perovskite layer by vacuum evaporation, wherein the rate of cesium bromide (CsBr) is 0.1 A / s, and the rate of lead iodide (PbI2) is 0.1 A / s. The total thickness is 1000 nm.

[0141] A mixed solution of FAI and FABr is prepared, and the molar concentration ratio of FAI to FABr is 3:1. The solvent is ethanol or isopropanol. 90 μL of the mixed solution of FAI and FABr is spin-coated on the layer of lead iodide and cesium bromide to react and form a second perovskite layer (3000 nm thick on average).

[0142] The second perovskite layer is annealed at a temperature of 200°C for 5 min to form a perovskite light absorption layer (3000 nm thick on average).

[0143] In the tenth step, a LiF thin film layer (1 nm thick) and a C60 thin film layer (10 nm thick) are sequentially prepared on the perovskite light absorption layer by vacuum evaporation as an electron transport interface layer (11 nm thick). 60

[0144] In the eleventh step, an electron transport layer (10 nm thick) of SnO2 is prepared by atomic deposition (ALD).

[0145] In the twelfth step, a second transparent conductive layer (100 nm thick) of ITO is formed on the electron transport layer by magnetron sputtering.

[0146] In the thirteenth step, a silver electrode is formed on the first transparent conductive layer and the second transparent conductive layer by screen printing.

[0147] Example Four

[0148] ​​​The fabrication method of the perovskite-n-type silicon-based tandem solar cell provided in this invention is as follows:

[0149] The first step involves providing a commercially available n-type silicon wafer with a resistivity of 3 Ω·cm, a thickness of 180 μm, and a texture size of 4 μm. The silicon wafer undergoes texturing and cleaning processes sequentially to form a textured n-type monocrystalline silicon substrate.

[0150] The second step involves using a PECVD device to deposit an intrinsic amorphous silicon passivation layer (5 nm thick) on both sides of an n-type monocrystalline silicon substrate, forming a first passivation layer on the front side of the n-type monocrystalline silicon substrate and a second passivation layer on the back side of the n-type monocrystalline silicon substrate.

[0151] The third step involves depositing phosphorus doping (doping concentration 10) on the first passivation layer using a PECVD device. 20 cm -3 The n-type amorphous silicon layer (10nm thick) forms the front emitter.

[0152] The fourth step involves depositing boron doping (doping concentration 10) on the second passivation layer using a PECVD device. 19 cm -3 A p-type amorphous silicon layer (10nm thick) forms the back field structure.

[0153] The fifth step involves fabricating a first transparent conductive layer (100 nm thick) of ITO material on a p-type amorphous silicon layer using magnetron sputtering.

[0154] The sixth step involves using a PECVD device to sequentially deposit an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer on the n-type amorphous silicon layer to form a tunneling composite layer (8 nm thick).

[0155] Step 7: A hole transport layer (15 nm thick) of spiro-TTB material is prepared on the tunneling composite layer using a vacuum evaporation process, with an evaporation rate of [missing information].

[0156] Step 8: Lead iodide and cesium bromide are formed on the hole transport layer using a vacuum evaporation process, wherein the cesium bromide (CsBr) deposition rate is [missing information]. The rate of lead iodide (PbI2) is Total thickness 400nm.

[0157] Step 9: A perovskite component (Cs) is spin-coated onto the hole transport layer with a textured surface using a spin-coating process. 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4A DMF / DMSO (4:1) solution of perovskite components, FAI and FABr, with a concentration of 1.2 mol / L for perovskite components, 0.5 mol / L for FAI, and 0.1 mol / L for FABr, was spin-coated at a rotation speed of 2000 rpm and treated with anisole extraction, followed by annealing at 120℃ for 20 min to form a perovskite light-absorbing layer (average thickness 550 nm).

[0158] In the tenth step, a LiF thin film layer (thickness 1 nm) and a C 60 thin film layer (thickness 10 nm) were sequentially prepared on the perovskite light-absorbing layer by a vacuum evaporation process as an electron transport interface layer (thickness 11 nm).

[0159] In the eleventh step, an electron transport layer (thickness 10 nm) of SnO2 material was prepared by an atomic deposition process (ALD).

[0160] In the twelfth step, a second transparent conductive layer (thickness 100 nm) of ITO material was formed on the electron transport layer by a magnetron sputtering process.

[0161] In the thirteenth step, a silver electrode was formed on the first transparent conductive layer and the second transparent conductive layer by a screen printing process.

[0162] Example Five

[0163] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiments of the present application is specifically described as follows:

[0164] In the first step, a commercial n-type silicon wafer with a resistivity of 3Ω.cm, a thickness of 180μm, and a texturing size of 4μm was provided. The silicon wafer was subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a textured surface.

[0165] In the second step, intrinsic amorphous silicon passivation layers (thickness 5nm) were deposited on both sides of the n-type monocrystalline silicon substrate by a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0166] In the third step, a phosphorus-doped (doping concentration 10 20 cm -3 ) n-type amorphous silicon layer (thickness 10nm) was deposited on the first passivation layer by a PECVD device to form a front emitter.

[0167] In the fourth step, a boron-doped (doping concentration 10 19 cm -3 ) p-type amorphous silicon layer (thickness 10nm) was deposited on the second passivation layer by a PECVD device to form a back field structure.

[0168] In the fifth step, a first transparent conductive layer (100 nm in thickness) of ITO is prepared on the p-type amorphous silicon layer by magnetron sputtering.

[0169] In the sixth step, an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer are sequentially deposited on the n-type amorphous silicon layer by a PECVD device to form a tunneling recombination layer (8 nm in thickness).

[0170] In the seventh step, a hole transport layer (15 nm in thickness) of spiro-TTB is prepared on the tunneling recombination layer by vacuum evaporation at an evaporation rate of 0.1 A / s.

[0171] In the eighth step, lead iodide and cesium bromide are formed on the hole transport layer by vacuum evaporation, wherein the rate of cesium bromide (CsBr) is 0.1 A / s. The rate of lead iodide (PbI2) is 0.1 A / s. The total thickness is 50 nm.

[0172] In the ninth step, a DMF / DMSO (4:1) solution of perovskite components (CsFAI3, FAI and FABr) is spin-coated on the hole transport layer with a textured structure at a concentration of 0.1 mol / L for the perovskite components, 0.1 mol / L for FAI and 0.5 mol / L for FABr at a rotation speed of 500 rpm, and then extracted by anisole, followed by annealing at 100°C for 30 min to form a perovskite light absorption layer (100 nm in average thickness). 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4

[0173] In the tenth step, a thin film layer (1 nm in thickness) of LiF and a thin film layer (10 nm in thickness) of C60 are sequentially prepared on the perovskite light absorption layer by vacuum evaporation as an electron transport interface layer (11 nm in thickness). 60

[0174] In the eleventh step, an electron transport layer (10 nm in thickness) of SnO2 is prepared by atomic deposition (ALD).

[0175] In the twelfth step, a second transparent conductive layer (100 nm in thickness) of ITO is formed on the electron transport layer by magnetron sputtering.

[0176] In the thirteenth step, a silver electrode is formed on the first and second transparent conductive layers by screen printing.

[0177] Example Six

[0178] ​​The fabrication method of the perovskite-n-type silicon-based tandem solar cell provided in this invention is as follows:

[0179] The first step involves providing a commercial-grade n-type silicon wafer with a resistivity of 3 Ω·cm, a thickness of 180 μm, and a texture size of 4 μm. The silicon wafer undergoes texturing and cleaning processes sequentially to form a textured n-type monocrystalline silicon substrate.

[0180] The second step involves using a PECVD device to deposit an intrinsic amorphous silicon passivation layer (5 nm thick) on both sides of an n-type monocrystalline silicon substrate, forming a first passivation layer on the front side of the n-type monocrystalline silicon substrate and a second passivation layer on the back side of the n-type monocrystalline silicon substrate.

[0181] The third step involves depositing phosphorus doping (doping concentration 10) on the first passivation layer using a PECVD device. 20 cm -3 The n-type amorphous silicon layer (10nm thick) forms the front emitter.

[0182] The fourth step involves depositing boron doping (doping concentration 10) on the second passivation layer using a PECVD device. 19 cm -3 A p-type amorphous silicon layer (10nm thick) forms the back field structure.

[0183] The fifth step involves fabricating a first transparent conductive layer (100 nm thick) of ITO material on a p-type amorphous silicon layer using magnetron sputtering.

[0184] The sixth step involves using a PECVD device to sequentially deposit an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer on the n-type amorphous silicon layer to form a tunneling composite layer (8 nm thick).

[0185] Step 7: A hole transport layer (15 nm thick) of spiro-TTB material is prepared on the tunneling composite layer using a vacuum evaporation process, with an evaporation rate of [missing information].

[0186] Step 8: Lead iodide and cesium bromide are formed on the hole transport layer using a vacuum evaporation process, wherein the cesium bromide (CsBr) deposition rate is [missing information]. The rate of lead iodide (PbI2) is Total thickness 1000nm.

[0187] Step 9: A perovskite component (Cs) is spin-coated onto the hole transport layer with a textured surface using a spin-coating process. 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4A DMF / DMSO (4:1) solution of perovskite components, FAI and FABr, with a concentration of 3 mol / L for perovskite components, 3 mol / L for FAI, and 3 mol / L for FABr, was spin-coated at a rotation speed of 6000 rpm and treated with anisole extraction, followed by annealing at 200℃ for 5 min to form a perovskite light-absorbing layer (average thickness 3000 nm).

[0188] In the tenth step, a LiF thin film layer (thickness 1 nm) and a C 60 thin film layer (thickness 10 nm) were prepared on the perovskite light-absorbing layer by vacuum evaporation process as an electron transport interface layer (thickness 11 nm).

[0189] In the eleventh step, an electron transport layer (thickness 10 nm) of SnO2 material was prepared by atomic deposition process (ALD).

[0190] In the twelfth step, a second transparent conductive layer (thickness 100 nm) of ITO material was formed on the electron transport layer by magnetron sputtering process.

[0191] In the thirteenth step, a silver electrode was formed on the first transparent conductive layer and the second transparent conductive layer by screen printing process.

[0192] Example Seven

[0193] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiments of the present application is described as follows:

[0194] In the first step, a commercial n-type silicon wafer with a resistivity of 3Ω.cm, a thickness of 180μm, and a texturing size of 4μm was provided. The silicon wafer was subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a texturing surface.

[0195] In the second step, intrinsic amorphous silicon passivation layers (thickness 5 nm) were deposited on both sides of the n-type monocrystalline silicon substrate by a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0196] In the third step, a phosphorus-doped (doping concentration 10 20 cm -3 ) n-type amorphous silicon layer (thickness 10 nm) was deposited on the first passivation layer by a PECVD device to form a front emitter.

[0197] In the fourth step, a boron-doped (doping concentration 10 19 cm -3 ) p-type amorphous silicon layer (thickness 10 nm) was deposited on the second passivation layer by a PECVD device to form a back field structure.

[0198] In the fifth step, a first transparent conductive layer (100 nm in thickness) of ITO is prepared on the p-type amorphous silicon layer by magnetron sputtering.

[0199] In the sixth step, an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer are sequentially deposited on the n-type amorphous silicon layer by a PECVD device to form a tunneling recombination layer (8 nm in thickness).

[0200] In the seventh step, a hole transport layer (15 nm in thickness) of spiro-TTB is prepared on the tunneling recombination layer by vacuum evaporation at an evaporation rate of 0.1 A / s.

[0201] In the eighth step, lead iodide and cesium bromide are formed on the hole transport layer by vacuum evaporation at a rate of 0.1 A / s for the cesium bromide (CsBr) and 0.1 A / s for the lead iodide (PbI2). The total thickness is 50 nm.

[0202] A FAI and FABr mixed solution is configured, the molar concentration ratio of the FAI and FABr is 3:1, and the solvent is ethanol or isopropanol. 90 μL of the FAI and FABr mixed solution is spin-coated on the lead iodide and cesium bromide layer to react, and then the first perovskite layer is annealed at a temperature of 100°C for 30 min to form a first perovskite layer (100 nm in average thickness).

[0203] In the ninth step, a DMF / DMSO (4:1) solution of perovskite components (Cs 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4 ) is spin-coated on the hole transport layer with a textured structure at a concentration of 0.1 mol / L and a rotation speed of 500 rpm, and then extracted by anisole, and then a perovskite light absorption layer (100 nm in average thickness) is formed by annealing at 70°C for 60 min.

[0204] In the tenth step, a LiF thin film layer (1 nm in thickness) and a C 60 thin film layer (10 nm in thickness) are sequentially prepared on the perovskite light absorption layer by vacuum evaporation as an electron transport interface layer (11 nm in thickness).

[0205] In the eleventh step, an electron transport layer (10 nm in thickness) of SnO2 is prepared by atomic deposition (ALD).

[0206] In the twelfth step, a second transparent conductive layer (100 nm in thickness) of ITO is formed on the electron transport layer by magnetron sputtering.

[0207] ​Thirteenth step, using screen printing process to form silver electrode on the first and second transparent conductive layer.

[0208] Example eight

[0209] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiment of the present application is specifically described as follows.

[0210] First step, providing a commercial n-type silicon wafer with a resistivity of 3 Ω·cm, a thickness of 180 μm and a texturing size of 4 μm. The silicon wafer is subjected to texturing and cleaning treatment in sequence to form an n-type monocrystalline silicon substrate with a textured surface.

[0211] Second step, depositing intrinsic amorphous silicon passivation layers (5 nm in thickness) on both sides of the n-type monocrystalline silicon substrate by using a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0212] Third step, depositing a phosphorus-doped (doping concentration 10 20 cm -3 ) n-type amorphous silicon layer (10 nm in thickness) on the first passivation layer by using a PECVD device to form a front emitter.

[0213] Fourth step, depositing a boron-doped (doping concentration 10 19 cm -3 ) p-type amorphous silicon layer (10 nm in thickness) on the second passivation layer by using a PECVD device to form a back field structure.

[0214] Fifth step, preparing a first transparent conductive layer (100 nm in thickness) made of ITO material on the p-type amorphous silicon layer by using a magnetron sputtering process.

[0215] Sixth step, depositing an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer in sequence on the n-type amorphous silicon layer by using a PECVD device to form a tunneling recombination layer (8 nm in thickness).

[0216] Seventh step, preparing an electron transport layer (15 nm in thickness) made of C 60 material on the tunneling recombination layer by using a vacuum evaporation process, and the evaporation rate is

[0217] Eighth step, forming lead iodide and cesium bromide on the electron transport layer by using a vacuum evaporation process, wherein the rate of cesium bromide (CsBr) is and the rate of lead iodide (PbI2) is and the total thickness is 1000 nm.

[0218] The FAI and FABr mixed solution is configured, the molar concentration ratio of the FAI and FABr is 3:1, and the solvent is ethanol or isopropanol. 90 μL of the FAI and FABr mixed solution is spin-coated on the lead iodide and cesium bromide layer and reacts, and then the first perovskite layer (average thickness 300 nm) is formed by annealing the first perovskite layer at a temperature of 200 ℃ for 5 min.

[0219] In the ninth step, a perovskite component (Cs 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4 ) DMF / DMSO (4:1) solution with a concentration of 3 mol / L is spin-coated on the electron transport layer with a textured structure at a spin speed of 6000 rpm, and then a perovskite light absorption layer (average thickness 300 nm) is formed by using anisole extraction treatment and annealing at 190 ℃ for 5 min.

[0220] In the tenth step, a hole transport layer (thickness 10 nm) made of spiro-TTB is evaporated on the perovskite light absorption layer by a vacuum evaporation process, and the evaporation rate

[0221] In the eleventh step, a buffer layer (thickness 10 nm) made of NiOx is prepared by an atomic layer deposition process (ALD).

[0222] In the twelfth step, a second transparent conductive layer (thickness 100 nm) made of ITO is formed on the hole transport layer by a magnetron sputtering process.

[0223] In the thirteenth step, a silver electrode is formed on the first transparent conductive layer and the second transparent conductive layer by a screen printing process.

[0224] Example Nine

[0225] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiment of the application is as follows:

[0226] In the first step, a commercial n-type silicon wafer with a resistivity of 3 Ω.cm, a thickness of 180 μm, and a textured size of 4 μm is provided. The silicon wafer is subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a texture.

[0227] In the second step, intrinsic amorphous silicon passivation layers (thickness 5 nm) are deposited on both sides of the n-type monocrystalline silicon substrate by using a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0228] The third step involves depositing phosphorus doping (doping concentration 10) on the first passivation layer using a PECVD device. 20 cm -3 The n-type amorphous silicon layer (10nm thick) forms the front emitter.

[0229] The fourth step involves depositing boron doping (doping concentration 10) on the second passivation layer using a PECVD device. 19 cm -3 A p-type amorphous silicon layer (10nm thick) forms the back field structure.

[0230] The fifth step involves fabricating a first transparent conductive layer (100 nm thick) of ITO material on a p-type amorphous silicon layer using magnetron sputtering.

[0231] The sixth step involves using a PECVD device to sequentially deposit an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer on the n-type amorphous silicon layer to form a tunneling composite layer (8 nm thick).

[0232] Step 7: Prepare C on the tunneling composite layer using a vacuum evaporation process. 60 The electron transport layer of the material (15nm thick) has an evaporation rate of

[0233] Step 8: Lead iodide and cesium bromide are formed on the electron transport layer using a vacuum evaporation process, wherein the cesium bromide (CsBr) deposition rate is... The rate of lead iodide (PbI2) is Total thickness 500nm.

[0234] A mixed solution of FAI and FABr was prepared, with a molar ratio of FAI to FABr of 3:1, using ethanol or isopropanol as the solvent. 90 μL of the FAI and FABr mixed solution was spin-coated onto the lead iodide and cesium bromide layers and allowed to react. The first perovskite layer was then annealed at 150 °C for 20 min to form the first perovskite layer (average thickness 200 nm).

[0235] The ninth step involves spin-coating a perovskite component (Cs) onto the electron transport layer with a textured surface using a spin-coating process. 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4 A DMF / DMSO (4:1) solution with a perovskite component concentration of 1.5 mol / L was prepared by spin coating at 3000 rpm and extracted with anisole. The perovskite light-absorbing layer (average thickness 3000 nm) was then formed by annealing at 130 °C for 30 min.

[0236] The tenth step is to evaporate a hole transport layer (10 nm in thickness) made of spiro-TTB on the perovskite light absorption layer by using a vacuum evaporation process, and the evaporation rate is 0.1 A / s.

[0237] The tenth step is to prepare a NiO x buffer layer (10 nm in thickness) made of the material.

[0238] The twelfth step is to form a second transparent conductive layer (100 nm in thickness) made of ITO on the hole transport layer by using a magnetron sputtering process.

[0239] The thirteenth step is to form a silver electrode on the first transparent conductive layer and the second transparent conductive layer by using a screen printing process.

[0240] Comparative Example 1

[0241] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiment of the present application is specifically described as follows.

[0242] The first step is to provide a commercial n-type silicon wafer with a resistivity of 3 Ω·cm, a thickness of 180 μm, and a texturing size of 4 μm. The silicon wafer is subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a texturing surface.

[0243] The second step is to deposit intrinsic amorphous silicon passivation layers (5 nm in thickness) on both sides of the n-type monocrystalline silicon substrate by using a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0244] The third step is to deposit an n-type amorphous silicon layer (10 nm in thickness) doped with phosphorus (10 20 cm -3 ) on the first passivation layer by using a PECVD device to form a front emitter.

[0245] The fourth step is to deposit a p-type amorphous silicon layer (10 nm in thickness) doped with boron (10 19 cm -3 ) on the second passivation layer by using a PECVD device to form a back field structure.

[0246] The fifth step is to prepare a first transparent conductive layer (100 nm in thickness) made of ITO on the p-type amorphous silicon layer by using a magnetron sputtering process.

[0247] The sixth step is to deposit an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer in sequence on the n-type amorphous silicon layer by using a PECVD device to form a tunneling recombination layer (8 nm in thickness).

[0248] The seventh step is to prepare a hole transport layer (15 nm in thickness) of spiro-TTB material on the tunneling composite layer by a vacuum evaporation process, and the evaporation rate is 0.1-0.2 A / s.

[0249] The eighth step is to form lead iodide and cesium bromide on the hole transport layer by a vacuum evaporation process, wherein the rate of cesium bromide (CsBr) is 0.1-0.2 A / s. The rate of lead iodide (PbI2) is 0.1-0.2 A / s. The total thickness is 400 nm.

[0250] A FAI and FABr mixed solution is configured, the molar concentration ratio of FAI and FABr is 3:1, and the solvent is ethanol or isopropanol. 80 μL of the FAI and FABr mixed solution is spin-coated on the lead iodide and cesium bromide layer to react and form a perovskite film (550 nm in thickness).

[0251] The perovskite film is annealed at a temperature of 150℃ for 20 min to form a perovskite light absorption layer (550 nm in thickness).

[0252] The ninth step is to prepare a LiF thin film layer (1 nm in thickness) and a C 60 The thin film layer (10 nm in thickness) is used as an electron transport interface layer (11 nm in thickness).

[0253] The tenth step is to prepare an electron transport layer (10 nm in thickness) of SnO2 material by an atomic deposition process (ALD).

[0254] The eleventh step is to form a second transparent conductive layer (100 nm in thickness) of ITO material on the electron transport layer by a magnetron sputtering process.

[0255] The twelfth step is to form a silver electrode on the first transparent conductive layer and the second transparent conductive layer by a screen printing process.

[0256] Comparative Example 2

[0257] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiment of the present application is specifically described as follows.

[0258] The first step is to provide a commercial n-type silicon wafer with a resistivity of 3Ω.cm, a thickness of 180 μm, and a textured surface size of 4 μm. The silicon wafer is subjected to texturing and cleaning processes in sequence to form an n-type monocrystalline silicon substrate with a textured surface.

[0259] The second step is to deposit intrinsic amorphous silicon passivation layers (5 nm in thickness) on both sides of the n-type monocrystalline silicon substrate by a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0260] Third step, depositing a phosphorus-doped (doping concentration 10 20 cm -3 ) n-type amorphous silicon layer (thickness 10 nm) on the first passivation layer to form a front emitter using a PECVD device.

[0261] Fourth step, depositing a boron-doped (doping concentration 10 19 cm -3 ) p-type amorphous silicon layer (thickness 10 nm) on the second passivation layer to form a back structure using a PECVD device.

[0262] Fifth step, preparing a first transparent conductive layer (thickness 100 nm) of ITO material on the p-type amorphous silicon layer using a magnetron sputtering process.

[0263] Sixth step, sequentially depositing an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer on the n-type amorphous silicon layer to form a tunneling recombination layer (thickness 8 nm) using a PECVD device.

[0264] Seventh step, preparing a hole transport layer (thickness 15 nm) of spiro-TTB material on the tunneling recombination layer using a vacuum evaporation process, with an evaporation rate of

[0265] Eighth step, spin-coating a DMF / DMSO (4:1) solution of perovskite components (Cs 0.05 FA 0.8 MA 0.15 PbBr 0.6 I 2.4 ) with a concentration of 2.1 mol / L on the hole transport layer with a textured structure at a spin speed of 2000 rpm, and using anisole extraction treatment, followed by annealing at 100°C for 20 min to form a perovskite light absorption layer (average thickness 2500 nm).

[0266] Ninth step, sequentially preparing a LiF thin film layer (thickness 1 nm) and a C 60 thin film layer (thickness 10 nm) as an electron transport interface layer (thickness 11 nm) on the perovskite light absorption layer using a vacuum evaporation process.

[0267] Tenth step, preparing an electron transport layer (thickness 10 nm) of SnO2 material using an atomic deposition process (ALD).

[0268] Eleventh step, forming a second transparent conductive layer (thickness 100 nm) of ITO material on the electron transport layer using a magnetron sputtering process.

[0269] Twelfth step, forming silver electrodes on the first and second transparent conductive layers using a screen printing process.

[0270] Comparative Example Three

[0271] The manufacturing method of the perovskite-n-type silicon-based stacked solar cell provided by the embodiment of the present application is specifically described as follows.

[0272] In the first step, a commercial n-type silicon wafer with a resistivity of 3 Ω·cm, a thickness of 180 μm and a texturing size of 4 μm is provided. The silicon wafer is subjected to texturing and cleaning successively to form an n-type monocrystalline silicon substrate with a texturing surface.

[0273] In the second step, an intrinsic amorphous silicon passivation layer (5 nm in thickness) is deposited on both sides of the n-type monocrystalline silicon substrate by using a PECVD device to form a first passivation layer on the front surface of the n-type monocrystalline silicon substrate and a second passivation layer on the back surface of the n-type monocrystalline silicon substrate.

[0274] In the third step, an n-type amorphous silicon layer (10 nm in thickness) doped with phosphorus (doping concentration 10 20 cm -3 ) is deposited on the first passivation layer by using a PECVD device to form a front surface emitter.

[0275] In the fourth step, a p-type amorphous silicon layer (10 nm in thickness) doped with boron (doping concentration 10 19 cm -3 ) is deposited on the second passivation layer by using a PECVD device to form a back surface field structure.

[0276] In the fifth step, a first transparent conductive layer (100 nm in thickness) made of ITO is prepared on the p-type amorphous silicon layer by using a magnetron sputtering process.

[0277] In the sixth step, an n-type doped microcrystalline silicon layer and a p-type doped microcrystalline silicon layer are successively deposited on the n-type amorphous silicon layer by using a PECVD device to form a tunneling recombination layer (8 nm in thickness).

[0278] In the seventh step, an electron transport layer (15 nm in thickness) made of C 60 is prepared on the tunneling recombination layer by using a vacuum evaporation process, and the evaporation rate is

[0279] In the eighth step, lead iodide and cesium bromide are formed on the electron transport layer by using a vacuum evaporation process, wherein the rate of cesium bromide (CsBr) is and the rate of lead iodide (PbI2) is and the total thickness is 400 nm.

[0280] An FAI and FABr mixed solution is configured, the molar concentration ratio of FAI and FABr is 3:1, and the solvent is ethanol or isopropanol. 80 μL of the FAI and FABr mixed solution is spin-coated on the lead iodide and cesium bromide layer to react and form a perovskite thin film (550 nm in thickness).

[0281] At a temperature of 150℃, the second perovskite layer is annealed for 20min to form a perovskite light absorption layer (thickness 550nm).

[0282] In the ninth step, a hole transport layer (thickness 10nm) made of spiro-TTB is prepared on the perovskite light absorption layer by vacuum evaporation process.

[0283] In the tenth step, a buffer layer (thickness 10nm) made of NiOx is prepared on the hole transport layer by atomic layer deposition (ALD) process.

[0284] In the eleventh step, a second transparent conductive layer (thickness 100nm) made of ITO is formed on the hole transport layer by magnetron sputtering process.

[0285] In the twelfth step, silver electrodes are formed on the first and second transparent conductive layers by screen printing process.

[0286] To verify the performance of the stacked solar cell, the photoelectric conversion efficiency, fill factor, open circuit voltage, short circuit current and other performance parameters of the devices prepared in Example 1, Example 4, Example 8, Comparative Example 1, Comparative Example 2 and Comparative Example 3 are tested under the same effective area, and the performance parameter comparison is shown in Table 1.

[0287]

[0288]

[0289] As shown in Table 1, compared with the conventional stacked solar cell prepared by only using solution method or vacuum evaporation method, the perovskite-silicon-based stacked solar cell provided by the embodiments of the present application has improved open circuit voltage and short circuit current, and the photoelectric conversion efficiency is also improved. Therefore, the perovskite-silicon-based stacked solar cell prepared by the manufacturing method provided by the embodiments of the present application can have high open circuit voltage and high short circuit current, and the photoelectric conversion efficiency is also improved.

[0290] In the description of the above embodiments, specific features, structures, materials or characteristics can be combined in any one or more embodiments or examples in a suitable manner.

[0291] The above description is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for manufacturing a perovskite-silicon based tandem solar cell, characterized by, The application relates to a preparation method of a perovskite-silicon-based laminated solar cell. The application provides a substrate, which comprises a silicon substrate cell with a surface structure, a charge recombination layer and a first carrier transport layer which are sequentially stacked; A perovskite light absorption layer formed by two perovskite layers, i.e., a first perovskite layer and a second perovskite layer, is formed on the first carrier transport layer with a surface structure; the first perovskite layer is prepared by a solution method, and the second perovskite layer is prepared by a vacuum evaporation perovskite skeleton method; When the average vertical distance from the lowest end to the highest end of the surface structure of the first carrier transport layer is L, the average thickness of the first perovskite layer prepared by the solution method is greater than 0 and less than or equal to 1 / 2L.

2. The method for fabricating a perovskite-silicon tandem solar cell according to claim 1, characterized in that, The method for forming the perovskite light absorption layer on the first carrier transport layer with a surface structure comprises the following steps: The first perovskite layer is prepared on the first carrier transport layer with a surface structure by a solution method; Then the second perovskite layer is prepared by a vacuum evaporation perovskite skeleton method.

3. The method for fabricating a perovskite-silicon tandem solar cell according to claim 1, characterized in that, The method for forming the perovskite light absorption layer on the first carrier transport layer with a surface structure comprises the following steps: The second perovskite layer is prepared on the first carrier transport layer with a surface structure by a vacuum evaporation perovskite skeleton method, and then the first perovskite layer is prepared by a solution method.

4. The method for fabricating a perovskite-silicon tandem solar cell according to claim 1, characterized in that, The method for forming the perovskite light absorption layer on the first carrier transport layer with a surface structure comprises the following steps: The first perovskite layer is prepared on the first carrier transport layer with a surface structure by a solution method; wherein the solution used in the solution method contains excess organic amine; during the formation of the first perovskite layer, the material in the perovskite skeleton reacts with the organic amine to form the second perovskite layer.

5. The method for fabricating a perovskite-silicon tandem solar cell according to any one of claims 1 to 4, characterized in that, The solute of the solution used in the solution method contains a mixed perovskite component Cs x FA y MA z PbBr m I n (x+y+z=1, m+n=3), the solvent contains one or more of N,N-dimethylformamide and dimethyl sulfoxide.

6. The method for fabricating a perovskite-silicon tandem solar cell according to any one of claims 1 to 4, characterized in that, The vacuum evaporation perovskite skeleton method comprises the following steps: a perovskite skeleton is formed by vacuum evaporation, and then the perovskite skeleton reacts with organic amine to form the second perovskite layer. The perovskite framework is a mixture formed by two or more than three PbX2and CsY, wherein X and Y are selected from one or more of Cl - , Br - , I - , SCN - , and the organic amine is one or more of formamidinium hydroiodide, methylamine bromide and formamidinium hydrobromide.

7. The method of claim 5, wherein the method further comprises: The concentration of the solution used in the solution method is 0.2 mol / L-3 mol / L.

8. The method for fabricating a perovskite-silicon tandem solar cell according to any one of claims 1 to 3, characterized in that, The vacuum evaporation perovskite skeleton method comprises the following steps: an organic amine solution is spin-coated on the perovskite skeleton, wherein the rotation speed is 500 rpm-6000 rpm, and the thickness of the perovskite skeleton ranges from 50 nm to 1000 nm.

9. The method for fabricating a perovskite-silicon tandem solar cell according to any one of claims 1 to 4, characterized in that, After the perovskite light absorption layer is formed, the preparation method of the perovskite-silicon-based laminated solar cell further comprises the following steps: a second carrier transport layer, a transparent conductive layer and an electrode are sequentially formed on the perovskite light absorption layer.

10. A perovskite-silicon based tandem solar cell, characterized by, The perovskite-silicon-based laminated solar cell is prepared by the preparation method of the perovskite-silicon-based laminated solar cell according to any one of claims 1-9.

11. The perovskite-silicon based tandem solar cell according to claim 10, characterized in that The first perovskite layer is distributed at least in the valley of the texture structure of the first carrier transport layer, and the average thickness of the first perovskite layer is less than or equal to 1 / 2 of the height of the texture structure; and part of the structure of the second perovskite layer is distributed at least on the slope and top of the texture structure, and maintains the same texture shape on the slope and top.

12. The perovskite-silicon based tandem solar cell of claim 10, wherein, The thickness of the first carrier transport layer ranges from 5 nm to 200 nm, and the average thickness of the perovskite light absorption layer ranges from 100 nm to 3000 nm.

13. The perovskite-silicon based tandem solar cell of claim 10, wherein, The average thickness of the first perovskite layer ranges from 100 nm to 300 nm, and the thickness of the second perovskite layer ranges from 100 nm to 3000 nm.

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