Method and device for fabricating integrated tandem photovoltaic modules

Abstract

The present invention may provide a method and a device for a tandem perovskite photovoltaic module. A perovskite photovoltaic module may include a plurality of perovskite photovoltaic cells configured to match the voltage output of other photovoltaic modules. The present invention may provide a mixed-composition perovskite layer. A solar cell fabricated using a mixed-composition perovskite layer may exhibit enhanced performance and stability.

Description

Technology Field Cross-reference

[0001] The present application relates to U.S. Provisional Patent No. 63 / 081,747 filed on September 22, 2020, U.S. Provisional Patent No. 63 / 081,750 filed on September 22, 2020, U.S. Provisional Patent No. 63 / 081,753 filed on September 22, 2020, U.S. Provisional Patent No. 63 / 081,758 filed on September 22, 2020, U.S. Provisional Patent No. 63 / 081,756 filed on September 22, 2020, U.S. Provisional Patent No. 63 / 081,755 filed on September 22, 2020, and U.S. Provisional Patent No. 63 / 081,752 filed on September 22, 2020, October 2020 U.S. Provisional Patent Application No. 63 / 090,636 filed on the 12th, U.S. Provisional Patent Application No. 63 / 090,642 filed on October 12, 2020, U.S. Provisional Patent Application No. 63 / 090,643 filed on October 12, 2020, U.S. Provisional Patent Application No. 63 / 126,481 filed on December 16, 2020, U.S. Provisional Patent Application No. 63 / 126,483 filed on December 16, 2020, U.S. Provisional Patent Application No. 63 / 159,277 filed on March 10, 2021, U.S. Provisional Patent Application No. 63 / 176,845 filed on April 19, 2021, U.S. Provisional Patent Application No. 63 / 176,845 filed on June 3, 2021 63 / 196,585, U.S. provisional patent application No. 63 / 196,601 filed on June 3, 2021, and U.S. patent application No. 16 / 953,247 filed on November 19, 2020, the contents of each of the above applications are incorporated herein by reference in their entirety. Background Technology background

[0002] Solar cells are electrical devices that convert light into electricity. Silicon solar cells can convert light with wavelengths greater than approximately 300 nanometers ("nm") and less than approximately 1100 nm into electricity. However, the conversion efficiency of silicon solar cells can progressively worsen as the wavelength of light decreases from 1100 nm. Additionally, silicon solar cells may not be able to convert light with wavelengths greater than approximately 1100 nm into electricity, because these wavelengths lack the energy required to overcome the bandgap of silicon.

[0003] In a tandem solar cell, two individual solar cells can be stacked on top of each other. The bottom cell can be a silicon solar cell, and the top cell can be made of a different material. The top cell can have a higher bandgap than the silicon solar cell. Therefore, the top cell can efficiently convert shorter wavelength light into electricity. The top cell can be transparent to longer wavelength light, which allows the underlying silicon solar cell to absorb such longer wavelength light and convert it into electricity. The problem to be solved

[0004] Light loss at the interface between the upper cell and the lower cell, and recombination loss in any layer of the upper or lower cell, can result in low-efficiency cells. Additionally, tandem solar cells can be difficult to manufacture. means of solving the problem outline

[0005] The present invention describes a tandem silicon-perovskite photovoltaic module and a method for manufacturing the same. The tandem silicon-perovskite photovoltaic module described herein may have a bottom silicon solar cell and a top perovskite solar cell. The perovskite solar cell may have a higher bandgap than the silicon solar cell. For example, the perovskite solar cell may have a bandgap of about 1.7 eV, and the silicon solar cell may have a bandgap of about 1.1 eV. Thus, the perovskite solar cell can efficiently convert short-wavelength light into electricity. The perovskite solar cell may be transparent to longer-wavelength light, which allows the underlying silicon solar cell to absorb the longer-wavelength light and convert it into electricity. Together, perovskite solar cells and silicon solar cells can efficiently convert a wider spectrum of light into electricity than a single solar cell (i.e., there may be less degradation loss in tandem cells than in single-cell solar modules at higher overall spectral efficiency). Adding perovskite solar cells can improve the resulting solar module through cost reduction, improved performance per module weight, and improved overall module performance.

[0006] The silicon solar cell may be a monocrystalline or polycrystalline silicon solar cell. The silicon solar cell may be a component of a conventional photovoltaic panel. The photovoltaic panel may have a back sheet on which the silicon solar cell is placed. An encapsulant may cover the top of the silicon solar cell to prevent exposure to dust and moisture. The photovoltaic panel may also have a top glass plate to provide additional protection to the silicon solar cell.

[0007] Perovskite solar cells can be deposited on the bottom surface of an upper glass plate. This may differ from the structure of conventional tandem photovoltaic modules where perovskite cells are simply placed on a silicon wafer. By depositing perovskite solar cells on the bottom surface of an upper glass plate, manufacturers can integrate perovskite solar cells into existing silicon solar panels without changing tools or processes. Instead, these manufacturers can replace the existing glass plate with a perovskite glass plate. In the present invention, the perovskite glass plate may be referred to as "active glass."

[0008] A perovskite solar cell may have a first transparent conductive oxide ("TCO") layer deposited on an upper glass plate, a hole transport layer ("HTL") deposited on the first TCO layer, a perovskite layer deposited on the HTL, an electron transport layer ("ETL") deposited on the perovskite layer, and a second TCO layer deposited on the ETL. The first and second TCO layers can serve as terminals of the perovskite solar cell. The ETL and HTL can facilitate electron and hole transport, respectively, while suppressing hole and electron transport, respectively. The perovskite layer can absorb light to generate charge carriers, resulting in voltage and current flow across the terminals of the perovskite solar cell.

[0009] Perovskite solar cells and silicon solar cells can be electrically insulated from each other, and each cell can have its own terminals. That is, a tandem photovoltaic module can be a four-terminal module. Perovskite solar cells and silicon solar cells can be connected in series or parallel by appropriately connecting their terminals. In the case of a series connection, current matching is possible between the perovskite solar cells and silicon solar cells. In the case of a parallel connection, voltage matching is possible between the perovskite solar cells and silicon solar cells.

[0010] The present invention also describes a method for manufacturing the aforementioned active glass. The active glass may comprise a perovskite layer formed by individually applying a perovskite precursor and subsequently annealing the precursor. A metallic lead layer may be deposited, followed by an inorganic halide layer (e.g., methylammonium iodide / formamidinium iodide), and then a halide (e.g., iodine). By applying various precursors in this manner, the same deposition equipment can be used for multiple layers, thereby reducing complexity and cost and enabling high-throughput manufacturing processes. Additionally, high-quality films can be produced by strictly controlling the various ratios of the precursors. Furthermore, various precursors can be deposited for each layer to improve film quality. For example, lead acetate can be applied to the lead layer to improve the integration of organic halides and halides into the lead layer. Similarly, various halides can be introduced to improve grain growth and other film properties. Perovskite precursors can be applied by various techniques, including ultrasonic spraying, blade coating, slot die coating, and physical vapor deposition. When combined with multiple 'shower head' type nozzles, ultrasonic spray-on can provide uniform and controlled application of precursors, thereby enabling the production of high-quality films that are substantially defect-free.

[0011] The present disclosure also provides a method for depositing first and second TCO layers on a perovskite solar cell. The TCO layers may be deposited on the perovskite solar cell via physical vapor deposition (PVD). The PVD of the TCO layers may occur in an inline manufacturing process. The inline manufacturing process may include a multi-process chamber where the deposition of a selected target material takes place on the perovskite solar cell. The multi-process chamber may include a single conveyor belt that carries the perovskite solar cell throughout the multi-process chamber. The inline manufacturing process may limit the exposure of the perovskite solar cell to the deposition process and direct exposure to ultraviolet (UV) light, and ultimately reduce the number of defects formed in the ETL and perovskite layers due to the TCO deposition process.

[0012] The present invention also provides a method for connecting the layers of a tandem photovoltaic module. The silicon and perovskite layers of the tandem module may be connected in different ways depending on the type of silicon solar cell used. Different connection methods can provide optimal performance for various types of silicon solar cells. The present invention also provides a method for manufacturing a tandem photovoltaic module in which the voltage output of the upper perovskite module and the lower silicon module is matched. The method may include laser scribing the perovskite layer to form a perovskite solar cell. Since differences in voltage output of various lower modules can be accounted for in the creation of the perovskite solar cell, the laser scribing may vary for each lower photovoltaic module. This level of control can improve efficiency by more closely matching the voltages between modules to reduce wasted voltage. Additionally, a wider range of lower modules can be used due to the flexibility provided by custom perovskite solar cell sizes.

[0013] In one aspect, the present invention provides a device comprising: a silicon solar cell having a first bandgap; a glass plate covering the silicon solar cell, the glass plate comprising an upper surface and a bottom surface; and a perovskite solar cell having a second bandgap, which is deposited on the bottom surface of the glass plate. In some embodiments, the silicon solar cell is electrically insulated from the perovskite solar cell. In some embodiments, the silicon solar cell comprises two terminals and the perovskite solar cell comprises two terminals. In some embodiments, the perovskite solar cell comprises a photoactive perovskite layer, wherein the photoactive perovskite layer comprises CH3NH3PbX3 or H2NCHNH2PbX3. In some embodiments, X is It includes iodides, bromides, chlorides, or combinations thereof. In some embodiments, the perovskite solar cell includes a first transparent conductive oxide (TCO) layer and a second TCO layer. In some embodiments, the first TCO layer and the second TCO layer are terminals of the perovskite solar cell. In some embodiments, the first TCO layer and the second TCO layer include indium oxide. In some embodiments, the perovskite solar cell includes an electron transport layer (ETL) including phenyl-C61-butyric acid methyl ester. In some embodiments, the perovskite solar cell includes a hole transport layer (HTL) including nickel oxide. In some embodiments, the device further comprises a plurality of silicon solar cells comprising silicon solar cells and a plurality of perovskite solar cells comprising perovskite solar cells, wherein the plurality of perovskite solar cells are laser-scribed onto an upper glass plate to voltage-match or current-match the plurality of perovskite solar cells to the plurality of silicon solar cells. In some embodiments, the upper glass plate has a surface area substantially corresponding to the surface area of ​​a 60- or 72-cell solar panel. In some embodiments, the upper surface of the upper glass plate includes an anti-reflective coating. In some embodiments, the upper surface of the upper glass plate includes polydimethylsiloxane (PDMS). In some embodiments, the PDMS includes 1:10 alumina PDMS, textured 1:50 alumina PDMS, or textured PDMS. In some embodiments, the bottom surface of the upper glass plate has a textured surface. In some embodiments, the device further includes an encapsulation material disposed between a silicon solar cell and a perovskite solar cell.In some embodiments, the encapsulant is selected from the group consisting of ethylene-vinyl-acetate (“EVA”), thermoplastic polyolefin (“TPO”), PDMS, silicone (translator’s note: Except where the original English word “silicone” is included in parentheses in this specification, “silicon” means “silicon,” i.e., the element “silicon”), and paraffin. In some embodiments, the silicon solar cell and the perovskite solar cell are electrically connected in parallel. In some embodiments, the silicon solar cell and the perovskite solar cell are electrically connected in series. In some embodiments, the second bandgap is about 1.5 to 1.9 electron volts (eV). In some embodiments, the device has a power conversion efficiency of at least about 30%. In some embodiments, the silicon solar cell is selected from the group consisting of a monocrystalline solar cell, a polycrystalline solar cell, a passivated emitter back contact (PERC) solar cell, an interlocked back contact (IBC) solar cell, and a heterojunction (HIT) solar cell with an intrinsic thin layer.

[0014] In another aspect, the present invention provides a device comprising a silicon solar cell having a first bandgap; and a perovskite solar cell having a second bandgap, wherein the perovskite solar cell is disposed adjacent to the silicon cell, and the device has a power conversion efficiency of at least about 26%. In some embodiments, the silicon solar cell is electrically insulated from the perovskite solar cell. In some embodiments, the silicon solar cell comprises two terminals and the perovskite solar cell comprises two terminals. In some embodiments, the perovskite solar cell comprises a photoactive perovskite layer, wherein the photoactive perovskite layer comprises CH3NH3PbX3 or H2NCHNH2PbX3. In some embodiments, X is It includes iodides, bromides, chlorides, or combinations thereof. In some embodiments, the perovskite solar cell includes a first transparent conductive oxide (TCO) layer and a second TCO layer. In some embodiments, the first TCO layer and the second TCO layer are terminals of the perovskite solar cell. In some embodiments, the first TCO layer and the second TCO layer include indium oxide, indium tin oxide, or aluminum zinc oxide. In some embodiments, the perovskite solar cell includes an electron transport layer (ETL) comprising phenyl-C61-butyric acid methyl ester or C60. In some embodiments, the perovskite solar cell includes a hole transport layer (HTL) comprising nickel oxide. In some embodiments, the device further includes an encapsulant disposed between the silicon solar cell and the perovskite solar cell. In some embodiments, the encapsulant is selected from the group consisting of ethylene-vinyl-acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, and paraffin. In some embodiments, the silicon solar cell and the perovskite solar cell are electrically connected in parallel. In some embodiments, the silicon solar cell and the perovskite solar cell are electrically connected in series. In some embodiments, the second bandgap is between about 1.5 and 1.9 electron volts (eV). In some embodiments, the silicon solar cell is selected from the group consisting of a monocrystalline solar cell, a polycrystalline solar cell, a passivated emitter rear contact (PERC) solar cell, an interdigitated back contact (IBC) cell, and a heterojunction with an intrinsic thin-layer (HIT) solar cell.

[0015] In another aspect, the present invention provides (a) up to about 0.6 watts per square meter (W / cm²) 2 (b) a step of depositing a buffer layer of a transparent conductive layer on a solar cell using a deposition energy of ); and (b) up to approximately 1 W / cm² 2A method for forming a transparent conductive layer of a solar cell is provided, comprising the step of depositing a bulk layer of a transparent conductive layer on a buffer layer using a deposition energy. In some embodiments, (a) and (b) involve a physical vapor deposition process. In some embodiments, the buffer layer is at least 5 nanometers thick. In some embodiments, the method further comprises the step of depositing a silver layer on the solar cell prior to step (a). In some embodiments, the silver layer is up to about 10 angstroms thick. In some embodiments, the method further comprises the step of annealing the transparent conductive layer.

[0016] In another aspect, the present invention comprises: (a) depositing a metallic lead (Pb) layer on the top glass of a solar cell by physical vapor deposition; (b) applying a methylammonium iodide (MAI) or formamidinium iodide (FAI) layer on the metallic Pb layer by ultrasonic spraying; and (c) exposing the MAI or FAI layer to iodine gas by moving a distribution unit across the MAI or FAI layer, wherein the distribution unit comprises a plurality of nozzles configured to provide iodine gas. In some embodiments, the method further comprises the step of applying a Pb salt to the metallic lead layer prior to step (b). In some embodiments, the lead salt comprises one or more salts selected from the group consisting of lead acetate (II), lead chloride (II), lead bromide (II), and lead iodide (II). In some embodiments, the MAI or FAI layer comprises a methylammonium chloride (MACl) additive. In some embodiments, the method further comprises the step of applying a phenylethyl ammonium iodide (PEAI) solution to the MAI or FAI layer. In some embodiments, steps (a)–(c) are performed in a chamber that does not react with iodine gas. In some embodiments, the chamber is made of glass. In some embodiments, the chamber is made of titanium. In some embodiments, the method further comprises the step of (d) performing one or more annealing operations to form a metal Pb layer, an MAI or FAI layer, and a perovskite layer from iodine gas. In some embodiments, the plurality of nozzles includes one or more shower head nozzles.

[0017] In another aspect, the present invention provides a method for forming a perovskite layer of a solar cell, comprising: (a) using an ultrasonic dispensing unit comprising a plurality of nozzles to apply a lead halide layer comprising lead iodide, lead bromide, and lead chloride to the solar cell; and (b) applying a methylammonium halide layer on the lead halide layer using the ultrasonic dispensing unit. In some embodiments, the lead halide layer comprises a greater weight of lead chloride than lead bromide.

[0018] In another aspect, the present invention provides a method comprising: (a) providing a silicon photovoltaic module having a first voltage output, wherein the silicon photovoltaic module comprises an upper glass panel; (b) forming a perovskite layer on the upper glass panel; (c) manufacturing one or more perovskite solar cells from the perovskite layer, wherein one or more perovskite solar cells generate a voltage substantially corresponding to the voltage output of the silicon photovoltaic module; and (d) electrically connecting the silicon photovoltaic module to one or more perovskite solar cells.

[0019] In some embodiments, the manufacturing process involves using a laser scribe to define one or more perovskite solar cells. In some embodiments, the one or more perovskite solar cells are a plurality of perovskite solar cells. In some embodiments, the plurality of perovskite solar cells are connected in series. In some embodiments, the method further comprises the step of applying a plurality of contacts to one or more perovskite solar cells to electrically couple the one or more perovskite solar cells. In some embodiments, the method further comprises the step of applying an encapsulant to one or more perovskite solar cells. In some embodiments, the encapsulant is a thermoplastic polyolefin. In some embodiments, the thermoplastic polyolefin is ethyl-vinyl acetate. In some embodiments, the method further comprises the step of applying an edge seal to one or more perovskite solar cells.

[0020] In another aspect, the present invention provides a tandem solar module. The tandem solar module is: (i) a plurality of silicon solar cells connected in series and (ii) a silicon solar panel comprising an upper glass plate wherein the plurality of silicon solar cells are connected in series and combined to have a first open circuit voltage; A perovskite solar panel disposed on the lower side of an upper glass plate of the silicon solar panel, wherein the perovskite solar panel comprises a plurality of segments, and each segment of the plurality of segments comprises a plurality of laser-scribe strips of perovskite, wherein the plurality of laser-scribe strips of perovskite within the segment are connected in series to generate a second open-circuit voltage substantially identical to a first open-circuit voltage; and An interconnect connecting the plurality of segments of the plurality of silicon solar cells and perovskite solar panels in parallel Includes

[0021] In some embodiments, the plurality of segments comprises about 10 to about 200 segments. In some embodiments, the silicon solar panel is a top contact solar panel, an integrated back contact solar panel, or a shingled solar panel. In some embodiments, the silicon solar panel and the perovskite solar panel are connected to the same junction box. In some embodiments, the silicon solar panel and the perovskite solar panel have substantially similar surface areas. In some embodiments, a plurality of laser scribe strips of perovskite are connected via a P1 / P2 / P3 scheme.

[0022] In another aspect, the present invention is MA n1 FA n2 Cs n3 A perovskite layer comprising the composition of PbX3, wherein MA is methylammonium and FA is formamidinium, n1, n2 and n3 are independently greater than 0 and less than 1, and n1 + n2 + n3 = 1, wherein the perovskite solar cell comprising the perovskite layer maintains a solar conversion efficiency of about 80% or more after 300 hours of illumination under one sun conditions in an air atmosphere of >25°C and <100°C.

[0023] In some embodiments, X is selected from the group consisting of fluorine, chlorine, bromine, and iodine. In some embodiments, X is a combination of two or more of fluorine, chlorine, bromine, and iodine. In some embodiments, n1 is about 0.001 to about 0.05. In some embodiments, n3 is about 0.001 to about 0.15. In some embodiments, the photovoltaic conversion efficiency is about 90% or more of the initial conversion efficiency value after 300 hours of irradiation under one sun condition. In some embodiments, the photovoltaic conversion efficiency is about 95% or more of the initial conversion efficiency value after 300 hours of irradiation under one sun condition. In some embodiments, the perovskite layer does not contain additional additives.

[0024] In another aspect, the present invention comprises the steps of: (a) providing a substrate; (b) applying a perovskite precursor to the substrate; and (c) annealing the perovskite precursor to form a perovskite layer, wherein the perovskite layer is an MA n1 FA n2 Cs n3 A method comprising the steps of: having a composition of PbX3, wherein n1, n2, and n3 are independently greater than 0 and less than 1, and n1 + n2 + n3 = 1, and the perovskite solar cell containing said perovskite maintains a solar conversion efficiency of about 80% or more after irradiation for 300 hours under 1 solar condition in an air atmosphere of >25℃ and <100℃; and (d) treating the perovskite layer by an encapsulation lamination process at a temperature of at least about 120℃.

[0025] In some embodiments, the perovskite solar cell maintains at least about 80% of the initial conversion efficiency value after the encapsulation lamination process. In some embodiments, the perovskite solar cell maintains at least about 97% of the initial conversion efficiency value after the encapsulation lamination process. In some embodiments, the perovskite precursor is applied via an ultrasonic spraying process. In some embodiments, the annealing process includes heating the perovskite layer to a temperature of at least about 40-120°C.

[0026] In another aspect, the present invention is MA n1 FA n2 Cs n3 A perovskite layer comprising the composition of PbX3, wherein MA is methylammonium and FA is formamidinium, n1 is about 0.01 to 0.03, n2 is about 0.82 to 0.94, n3 is about 0.05 to 0.015, and n1+n2+n3=1.

[0027] In some embodiments, X is selected from the group consisting of fluorine, chlorine, bromine, and iodine. In some embodiments, X is a combination of two or more of fluorine, chlorine, bromine, and iodine. In some embodiments, the perovskite solar cell does not contain additional additives.

[0028] Another aspect of the present disclosure provides a method for assembling and manufacturing the elements and components described above and elsewhere in the present disclosure.

[0029] Further aspects and advantages of the present invention will be readily apparent to those skilled in the art from the following detailed description, in which only exemplary embodiments of the present invention are illustrated and described. As is understood, other and different embodiments of the present invention are possible, and some details thereof may be modified in various obvious aspects without departing from the invention. Accordingly, the drawings and description should be considered illustrative in nature and not restrictive. Integration by reference

[0030] All publications, patents, and patent applications mentioned in this specification are incorporated herein by reference to the same extent as each individual publication, patent, or patent application is specifically and individually incorporated by reference. To the extent that the incorporated publications and patents or patent applications conflict with the disclosures contained in this specification, this specification replaces and / or prioritizes such conflicting materials. Brief explanation of the drawing

[0031] Novel features of the present invention are described in particular in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by referring to the following detailed description and the accompanying drawings (in this document, “Drawings” and “Figures”), which describe exemplary embodiments in which the principles of the present invention are utilized. In the accompanying drawings:

[0032] FIG. 1 schematically illustrates a tandem, four-terminal, silicon-perovskite solar cell according to one embodiment.

[0033] FIG. 2 schematically illustrates the formation of a perovskite layer of a solar cell according to one embodiment.

[0034] FIG. 3 is a flowchart of the manufacturing process of a perovskite photovoltaic cell according to one embodiment of the present invention.

[0035] FIG. 4 is a flowchart of process 310 of FIG. 3 according to one embodiment.

[0036] FIG. 5 is a flowchart of process 340 of FIG. 3 according to one embodiment.

[0037] FIG. 6 is a flowchart of process 350 of FIG. 3 according to one embodiment.

[0038] FIG. 7 is a flowchart of process 360 of FIG. 3 according to one embodiment.

[0039] FIG. 8 schematically illustrates a perovskite precursor deposition chamber according to one embodiment.

[0040] FIG. 9 schematically illustrates a shower head design for a spray nozzle according to one embodiment.

[0041] FIG. 10 schematically illustrates the integrated manufacturing flow of a perovskite photovoltaic cell according to one embodiment.

[0042] FIG. 11 illustrates light transmission of various wavelengths through a perovskite solar cell according to one embodiment.

[0043] FIG. 12 shows a computer system programmed or configured to implement the method provided herein.

[0044] FIG. 13 is a flowchart of a manufacturing process for forming a perovskite layer according to one embodiment.

[0045] FIG. 14 illustrates a horizontal inline manufacturing system according to one embodiment.

[0046] FIG. 15 is a graph showing the current-voltage performance of a photovoltaic module manufactured with or without an ultrathin silver layer according to one embodiment.

[0047] Figures 16–19 show examples of various electrical network connections for various types of silicon-perovskite hybrid photovoltaic modules according to some embodiments.

[0048] FIG. 20 is a flowchart of a process for manufacturing a tandem solar module according to some embodiments.

[0049] FIG. 21 is a graph showing the efficiency of three types of perovskite solar cells during a reliability test at 85°C and 85% relative humidity according to one embodiment.

[0050] FIGS. 22A-22B illustrate examples of efficiency degradation of a perovskite solar cell under a maximum power point thermal stress test, a dark thermal stress test, and 1-solar illumination according to one embodiment.

[0051] FIGS. 23A-23C show graphs of open, short, and maximum power point efficiency for various temperatures in a perovskite solar cell according to one embodiment.

[0052] FIGS. 24A to 24B illustrate examples of devices for producing a perovskite layer that include the use of an antisolvent and do not use an antisolvent, respectively, according to some embodiments.

[0053] FIG. 25 illustrates an exemplary histogram of the efficiency of various perovskite layers produced by the method and system described herein according to one embodiment.

[0054] FIG. 26 is a schematic diagram of an exemplary photovoltaic module package according to an embodiment.

[0055] FIG. 27 is a schematic diagram of an example wiring diagram for a module package according to one embodiment. Specific details for implementing the invention details

[0056] Although various embodiments of the present invention have been illustrated and described herein, it will be apparent to those skilled in the art that such embodiments are provided merely as examples. Various modifications, changes, and substitutions may be made by those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be adopted.

[0057] Whenever the terms "at least," "greater than," or "greater than or equal to (or greater than)" come before the first number of a series of two or more numeric values ​​(or before the last number in the translation), the terms "at least," "greater than," or "greater than or equal to (or greater than)" apply to each of the numeric values ​​in the series. For example, 1, 2, or 3 or greater is 1 or greater, 2 or greater, or 3 or greater.

[0058] Whenever the terms "less than," "less than," or "less than" come before the first number of a series of two or more numerical values ​​(or before the last number in the translation), the terms "less than," "less than," or the expression "less than or equal to" apply to each of the numerical values ​​in the series. For example, the expression 3, 2, or 1 or less is 3 or less, 2 or less, or 1 or less.

[0059] As used in this specification, the term "solar cell" generally refers to a device that generates electricity from light using the photovoltaic effect.

[0060] The term "tandem" as used in this specification refers to a photovoltaic module having two solar cells stacked on top of each other.

[0061] The term “4-terminal” as used in this specification refers to a tandem solar module in which the upper and lower solar cells each have two accessible terminals.

[0062] In this specification, the term "perovskite" generally refers to a material having a crystal structure similar to calcium titanium oxide and suitable for use in perovskite solar cells. A general chemical term for perovskite materials is ABX3. Examples of perovskite materials include methylammonium lead trihalide (i.e., CH3NH3PbX3, where X is a halogen ion such as iodide, bromide, or chloride) and formamidinium lead trihalide (i.e., H2NCHNH2PbX3, where X is It includes halogen ions such as iodide, bromide, or chloride.

[0063] As used herein, the term “single-crystal silicon” generally refers to silicon having a uniform crystal structure throughout the material. The orientation, lattice parameters, and electronic properties of single-crystal silicon may be constant throughout the material. Single-crystal silicon may be doped with phosphorus or boron, for example, to make the silicon n-type or p-type, respectively.

[0064] As used in this specification, the term "polycrystalline silicon" generally refers to silicon having an irregular particle structure.

[0065] As used herein, the term "PERC (passivated emitter rear contact) solar cell" generally refers to a solar cell having an additional dielectric layer on the rear side. This dielectric layer can serve to reflect unabsorbed light back to the solar cell for a second absorption attempt, and additionally, passivate the rear side of the solar cell to increase the efficiency of the solar cell.

[0066] As used herein, the term “heterojunction having a high-intensity thin-layer solar cell (HIT)” generally refers to a solar cell composed of a single-crystal silicon wafer surrounded by an ultrathin amorphous silicon layer. One amorphous silicon layer may be n-doped and the other may be p-doped.

[0067] As used herein, the term “intersecting back contact cell (IBC)” generally refers to a solar cell comprising two or more electrical contacts disposed on the back of the solar cell (e.g., the side opposite to the incident light). The two or more electrical contacts may be disposed alternately adjacent to n- and p-doped regions of the solar cell. The IBC may comprise a high-quality absorbing material configured to allow carrier transport over long distances.

[0068] As used herein, the terms "band gap" and "band gap" generally refer to the energy difference between the top of the valence band and the bottom of the conduction band in a material.

[0069] The term "electron transport layer" ("ETL") as used herein generally refers to a layer of material that facilitates electron transport and inhibits hole transport in a solar cell. Electrons may be majority carriers and holes may be minority carriers in the ETL. The ETL may consist of one or more n-type layers. One or more n-type layers may include n-type excitation blocking layers. The n-type exciton blocking layer may have a wider bandgap than the photoactive layer of the solar cell (e.g., a perovskite layer) but may have a conduction band that is nearly identical to the conduction band of the photoactive layer. This allows electrons to easily pass from the photoactive layer to the ETL.

[0070] The n-type layer may be a metal oxide, a metal sulfide, a metal selenide, a metal telluride, amorphous silicon, an n-type group IV semiconductor (e.g., germanium), an n-type group III-V semiconductor (e.g., gallium arsenide), an n-type group II-VI semiconductor (e.g., cadmium selenide), an n-type group I-VII semiconductor (e.g., cuprous chloride), an n-type group IV-VI semiconductor (e.g., lead selenide), an n-type group V-VI semiconductor (e.g., bismuth telluride), or an n-type group II-V semiconductor (e.g., cadmium arsenide), any of which may be doped (e.g., with phosphorus, arsenic, or antimony) or not doped. The metal oxide may be an oxide of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or an oxide of a mixture of two or more of these metals. Metal sulfides may be sulfides of cadmium, tin, copper, zinc, or sulfides of a mixture of two or more of these metals. Metal selenides may be selenides of cadmium, zinc, indium, gallium, or a mixture of two or more of these metals. Metal tellurides may be tellurides of cadmium, zinc, cadmium, or tin, or tellurides of a mixture of two or more of the said metals. Alternatively, other n-type materials, including organic and polymeric electron transport materials and electrolytes, may be used. Suitable examples include, but are not limited to, organic electron transport materials comprising fullerene or fullerene derivatives (e.g., phenyl-C61-butyric acid methyl ester, C60, etc.) or perylene or derivatives thereof.

[0071] As used herein, the term "hole transport layer" ("HTL") generally refers to a layer of material that promotes hole transport and inhibits electron transport in a solar cell. Holes can be majority carriers in the HTL, whereas electrons can be minority carriers. The HTL may consist of one or more p-type layers. One or more p-type layers may include a p-type excitation blocking layer. The p-type exciton blocking layer may have a valence band that closely matches the valence band of the photoactive layer (e.g., a perovskite layer) of the solar cell. This allows holes to easily pass from the photoactive layer to the HTL.

[0072] The p-type layer may consist of a molecular hole transporter, a polymer hole transporter, or a copolymer hole transporter. For example, the p-type layer may be one or more of nickel oxide, thiophenyl, phenelenyl, dithiazolyl, benzothiazolyl, diketopyrrolopyrrolyl, ethoxydithiophenyl, amino, triphenylamino, carbozolyl, ethylenedioxythiophenyl, dioxythiophenyl, or fluorenyl. Additionally or alternatively, the p-type is Spiro-OMeTAD (2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene)), P3HT (poly(3-hexylthiophene)), PCPDTBT (poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2,6-diyl]]), PVK (poly(N-vinylcarbazole)), poly(3-hexylthiophene), poly[N,N-diphenyl-4-methoxyphenylamine-4',4"-diyl], hexathiophene, 9,10-bis(phenylethynyl)anthracene, 5,12-bis(phenylethynyl)naphthacene, It may include didenoperylene, 9,10-diphenylanthracene, PEDOT-TMA, PEDOT:PSS, perfluoropentacene, perylene, poly(phenylene oxide), poly(p-phenylene sulfide), quinacridone, rubrene, 4-(dimethylamino)benzaldehyde diphenylhydrazone, 4-(dibenzylamino)benzaldehyde-N,N-diphenylhydrazone, or phthalocyanine.

[0073] Although described herein in relation to silicon-perovskite tandem photovoltaic modules, the method and device of the present invention may be used with any combination of a solar cell and a perovskite layer. For example, the tandem photovoltaic module may be a tandem CdTe-perovskite photovoltaic module. In another example, the tandem photovoltaic module may be a dye-sensitized solar cell-perovskite solar cell module.

[0074] FIG. 1 schematically illustrates a tandem, four-terminal, silicon-perovskite photovoltaic module (100) according to an embodiment of the present invention. The photovoltaic module (100) may have an upper glass plate (105), a first TCO layer (110), an HTL (115), a perovskite layer (120), an ETL (125), a second TCO layer (130), an encapsulation material (135), a silicon solar cell (140), and a back plate (145).

[0075] The upper glass plate (105) can protect the lower layer of the solar module (100) from dust and moisture. The upper glass plate (105) and the solar module (100) may have a form factor corresponding to a conventional silicon solar panel overall. For example, the upper glass plate (105) may have a form factor corresponding to a 32-cell, 36-cell, 48-cell, 60-cell, 72-cell, 96-cell, or 144-cell silicon solar panel. The upper glass plate (105) may have a thickness of at least about 2.0 millimeters (mm), 2.5 mm, 3.0 mm, 3.5 mm, 4.0 mm, 4.5 mm, 5.0 mm, or more. The upper glass plate (105) may have a thickness of up to about 5.0 mm, 4.5 mm, 4.0 mm, 3.5 mm, 3.0 mm, 2.5 mm, or 2.0 mm. The upper glass plate (105) may be transparent so that light can access the solar cell underneath. In some cases, the upper surface of the upper glass plate (105) may be covered with polydimethylsiloxane ("PDMS") (e.g., 1:10 alumina PDMS, textured 1:50 alumina PDMS, or textured PDMS), which can improve light trapping and refractive index matching. In some cases, the upper surface of the upper glass plate (105) may be covered with an anti-reflective coating. In some cases, the bottom surface of the upper glass plate (105) may be textured with a perovskite layer (120) to enable more light scattering.

[0076] The first TCO layer (110), HTL (115), perovskite layer (120), ETL (125), and second TCO layer (130) together can form a perovskite solar cell. The perovskite solar cell can be placed on the bottom surface of the upper glass plate (105) through a manufacturing method described with reference to FIGS. 3 through 10. The perovskite solar cell can have a higher bandgap than the silicon solar cell (140). For example, the band gap of a perovskite solar cell is approximately 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73, 1.74, 1.75, 1.76, 1.77, 1.78, 1.79, 1.80, 1.81, 1.82, 1.83, 1.84, 1.85, 1.86, 1.87, 1.88, 1.89, 1.90, 1.91, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98, 1.99, 2.00, 2.01, 2.02, 2.03, 2.04, 2.05, 2.06, 2.07, 2.08, The electron volts ("eV") can be 2.09, 2.10 or higher. In contrast, silicon solar cells can have a band gap of about 1.1 eV. Therefore, perovskite solar cells can efficiently convert short-wavelength light into electricity. Perovskite solar cells can be transparent to longer-wavelength light, which allows the underlying silicon solar cell to absorb and convert longer-wavelength light into electricity. When perovskite solar cells and silicon solar cells are used together, a wider spectrum of light can be efficiently converted into electricity than with a single solar cell.

[0077] The first TCO layer (110) can be placed directly on the upper glass plate (105). Depositing the first TCO layer (110) directly on the upper glass plate (105) can prevent damage to the HTL (115) and the perovskite layer (120). The first TCO layer (110) can serve as the positive terminal or cathode of the perovskite solar cell. The first TCO layer (110) can have a thickness of at least about 100 nanometers (nm), 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, or 1 micrometer or more. The first TCO layer (110) may have a thickness of up to about 1 micrometer, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, or 100 nm. The first TCO layer (110) may be made of ITO (Indium Tin Oxide). The first TCO layer (110) may be made of doped ITO. The TCO layer may have a resistance of at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 ohms / square meter. The TCO layer can have a resistance of up to approximately 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 ohm / square meter.

[0078] The HTL (115) may be placed on the TCO layer (110). The HTL (115) can facilitate hole transport from the perovskite layer (120) to the first TCO layer (110) without compromising transparency and conductivity. In contrast, the HTL (115) can suppress electron transport. In some embodiments, the HTL (115) consists of one or more nickel oxide layers. In other embodiments, the HTL (115) is made of another suitable p-type material described herein. HTL (115) may have a thickness of at least about 5 nm, 10 nm, 20 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, or 1 micrometer or more, and HTL (115) may have a thickness of at most about 1 micrometer, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 50 nm, 20 nm, 10 nm, or 5 nm or less.

[0079] A perovskite layer (120) may be disposed on a hole transport layer (115). The perovskite layer (120) may be a photoactive layer of a perovskite solar cell. That is, the perovskite layer (120) may absorb light and generate holes and electrons, which can then diffuse to the HTL (115) and ETL (125), respectively. In some embodiments, the perovskite layer (120) is prepared from methylammonium lead triiodide, methylammonium lead tribromide, methylammonium lead trichloride, or any combination thereof. In other embodiments, the perovskite layer (120) is prepared from formamidinium lead triiodide, formamidinium lead tribromide, formamidinium lead trichloride, or any combination thereof. In another embodiment, the perovskite layer (120) is prepared from cesium lead triiodide, cesium lead tribromide, cesium lead trichloride, or any combination thereof. In some embodiments, the perovskite layer may be a trication perovskite material having different proportions of formamidinium, methylammonium, and cesium cations. Incorporating cesium into the perovskite lattice provides enhanced thermodynamic stability. The bandgap of the perovskite layer (120) can be adjusted by controlling the halide content of the methylammonium lead trihalide or the formamidinium lead trihalide. The perovskite layer (120) may have a thickness of at least about 250 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 micrometer, 1.25 micrometers, 1.5 micrometers, 1.75 micrometers, or 2 micrometers. The perovskite layer (120) may have a thickness of up to about 2 micrometers, 1.75 micrometers, 1.5 micrometers, 1.25 micrometers, 1 micrometer, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, or 250 nm.

[0080] An electron transport layer (125) may be disposed on a perovskite layer (120). The ETL (125) can facilitate electron transport from the perovskite layer (120) to the second TCO layer (130) without compromising transparency and conductivity. In contrast, the ETL (115) can inhibit electron transport. In some embodiments, the ETL (125) is made of phenyl-C61-butyric acid methyl ester ("PCBM"). In other embodiments, the ETL (125) is made of another suitable n-type material (e.g., C60) described herein. The ETL (115) may have a thickness of at least about 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm or more. The ETL (115) may have a thickness of up to about 500 nm, 400 nm, 300 nm, 200 nm, 100 nm, 90 nm, 80 nm, 70 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 10 nm or less. The interface between the ETL and the perovskite layer may be important for the performance of the perovskite layer. The surface of the perovskite layer may be hydrophilic to enable good coverage of hydrophilic ETL (e.g., PCBM). A combination of environmental factors (e.g., low humidity <15%, low temperature of 18–24 degrees Celsius) and solvent compatibility may affect the quality of the perovskite layer-ETL linkage.

[0081] The second TCO layer (130) may be disposed on the electron transport layer (125). The second TCO layer (130) may serve as a negative terminal or an anode of a perovskite solar cell. The second TCO layer (130) may have a thickness of at least about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, or 1 micrometer. The second TCO layer (130) may have a thickness of up to about 1 micrometer, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, 400 nm, 300 nm, 200 nm, or 100 nm. The second TCO layer (110) may be made of ITO (Indium Oxide). The second TCO layer (110) can be made of doped ITO.

[0082] The encapsulation material (135) can be placed between the second TCO layer (130) of the perovskite solar cell and the silicon solar cell (140). The encapsulation material (135) can prevent the perovskite solar cell and the silicon solar cell (140) from being exposed to dust and moisture. The encapsulation material (135) can electrically isolate the perovskite solar cell from the silicon solar cell (140). The encapsulation material (135) can have a high refractive index (e.g., greater than 1.4) that matches the refractive index of the TCO layer (130) of the perovskite solar cell and the upper silicon nitride or TCO layer of the silicon solar cell (140). Thus, the high refractive index material can improve the current density of the photovoltaic module (100) by reducing transmission losses between the TCO layer (130), the encapsulation material (135), and the silicon solar cell (140). Users of high refractive index materials can also improve light trapping. High refractive index materials may be ethylene-vinyl-acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, paraffin, etc. Example 1 and Fig. 9, described later, show improvements achieved by using a specific high refractive index material in the encapsulant (135). The encapsulant may be a TCO layer. For example, the TCO layer may cover the perovskite layer to protect it from external conditions (e.g., water, oxygen, etc.). In this example, the reliability of the integrated tandem module can be improved by using a TCO layer as the encapsulant. The encapsulant may include ethylene-vinyl-acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, paraffin, etc. The encapsulation layer can isolate perovskite solar cells and silicon solar cells from the surrounding environment. For example, the encapsulation material can encapsulate both the perovskite layer and the silicon layer simultaneously. The encapsulation layer can be configured to prevent the volatilization of one or more components of the perovskite layer.For example, the encapsulant can minimize the loss of organic cations (e.g., methylammonium, formamidinium, etc.) due to heating of the perovskite layer. In another example, the encapsulant can reduce the efflux of chemical species, such as lead iodide or other lead halides, from the perovskite layer (such efflux can lead to a decrease in the reliability of the integrated tandem module). The encapsulant can be treated to have sufficient crosslinking to protect the perovskite layer from water, oxygen, volatilization of organic compounds in the perovskite layer, or any combination thereof. The encapsulant can have a crosslinking percentage of at least about 50, 60, 70, 80, 90, or 95 percent. The encapsulant can have a crosslinking percentage of up to about 95, 90, 80, 70, 60, or 50 percent.

[0083] Generally, silicon solar cells (140) It may be a p-type silicon solar cell in which a p-type substrate is covered with a thin n-type layer ("emitter"), or an n-type silicon solar cell in which an n-type substrate is covered with a thin p-type layer emitter. The silicon solar cell (140) may be a single-crystal silicon solar cell, a polycrystalline silicon solar cell, a PERC silicon solar cell, a HIT silicon solar cell, an IBC (Interdigitated Back Contact Cell), etc.

[0084] The silicon solar cell (140) may include a back sheet (145). The back sheet (145) may seal the solar module (100) to prevent moisture penetration. In some cases, the back sheet (145) may be a glass plate having an upper surface and a bottom surface. The upper surface of the glass plate may have a highly reflective coating or a textured surface to further increase light trapping or scattering in the silicon solar cell (140) and the perovskite layer (120). The glass plate may be transparent. The glass plate may be substantially transparent. The transparency of the glass plate may facilitate bifacial operation of the solar cell. For example, the solar cell may be configured to absorb light from both sides of the solar cell.

[0085] The perovskite solar cells and silicon solar cells (140) can be electrically insulated from each other, and each cell can have its own terminals. That is, the tandem solar module can be a four-terminal module. The perovskite solar cells and silicon solar cells (140) can be connected in series or in parallel by appropriately connecting their terminals. In the case of a series connection, the perovskite solar cells and silicon solar cells can be current-matched. In the case of a parallel connection, the perovskite solar cells and silicon solar cells can be voltage-matched. Laser scribing can be used to achieve current-matching or voltage-matching by connecting individually scribed perovskite solar cells in series or in parallel to obtain the desired voltage or current. The parallel or series connection between the perovskite solar cells and silicon solar cells can be made via busbars / electrodes before module lamination. This allows for quick and easy introduction into existing silicon manufacturing processes.

[0086] The solar module (100) can have a power conversion efficiency of at least about 25%, 26%, 27%, 28%, 29%, 30% or more.

[0087] FIG. 2 schematically illustrates how the perovskite layer (120) of FIG. 1 is formed. A metallic Pb layer can be deposited on the HTL via physical vapor deposition. Next, MAI (Methylammonium iodide) or FAI (formamidinium iodide) can be applied to the metallic Pb layer. Finally, the MAI or FAI can be exposed to iodine gas to form a perovskite layer (120), which may be methylammonium lead triiodide or formamidinium lead triiodide. This process and other manufacturing processes will be described in more detail in subsequent drawings. TCO production

[0088] The first TCO layer (110) and the second TCO layer (130) can serve as electrical contacts for the perovskite solar cell so that the underlying silicon solar cell (140) can still absorb light while maintaining the translucency of the perovskite solar cell. A physical vapor deposition (PVD) process may be used to manufacture the first TCO layer (110) and the second TCO layer (130). The PVD process may be adjusted so that the resulting TCO layer is transparent to light (e.g., light with a wavelength of 300 nanometers ("nm") to 1200 nm for the second TCO layer). For example, the argon pressure and deposition power of the PVD process may be adjusted accordingly. For example, the argon pressure may be about 1 to about 5 millitors, and the deposition power may be about 20 watts to about 100 watts. Additionally, the thickness of the first TCO layer (110) and the second TCO layer (130) can be set to achieve such transparency. Such transparency may allow the lower silicon solar cell (140) to absorb as much light as possible that has not already been absorbed by the perovskite layer (120), which generally absorbs light having a wavelength of 300 nm to 700 nm.

[0089] In manufacturing the second TCO layer (130), the PVD process tends to create defects in the ETL (125) and the perovskite layer (120) due to ultraviolet and argon / oxygen ions generated by the plasma during the process. These defects can degrade the performance of the perovskite layer (120) as an electron-hole pair absorber. For example, the perovskite layer (120) may exhibit a lower open-circuit voltage and a lower fill factor as a result of these defects. It may be beneficial to minimize the generation of such defects.

[0090] In one embodiment, the damage described above can be minimized by first creating a buffer layer of TCO on the ETL (125) through a low-power PVD process. During the low-power PVD process, the power is up to about 0.60, 0.55, 0.50, 0.45, 0.40, 0.35, 0.30, 0.25, 0.20, 0.15, 0.10, 0.05 watts ("W / cm²) per square centimeter. 2 The thickness of the buffer layer may be less than or equal to 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65 nm. The thickness of the buffer layer may be less than or equal to 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5 nm. UV damage is generally generated by high-power ions that penetrate deep into the bulk of the ETL (125) and perovskite layer (120), breaking or damaging molecular bonds and causing degradation in both open-circuit voltage and series resistance. By using low-power PVD to create the buffer layer, high-energy ions can be blocked from reaching the ETL (125) and perovskite layer (125) in subsequent process steps.

[0091] The TCO bulk layer is up to 1.00, 0.95, 0.90, 0.85, 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45 W / cm 2 It can be deposited on the buffer layer of the TCO at the following deposition energy.

[0092] In some cases, an ultrathin layer of silver may be deposited at the interface between the ETL (125) and the second TCO layer (130) by deposition, sputtering, or atomic layer deposition. The ultrathin layer of silver may be up to about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 Angstrom thick. The ultrathin layer of silver may act as a barrier against ultraviolet rays or plasma during PVD of the second TCO layer (130). In some cases, post-annealing may be performed on the second TCO layer to partially repair some of the damage caused by ultraviolet rays or plasma during the PVD process. Post-annealing may be performed at 100 to 140 degrees for 2 to 4 minutes.

[0093] The TCO bulk layer is up to 0.90, 0.85, 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45 W / cm 2 It can be deposited on the buffer layer of the TCO with the following deposition energy.

[0094] Typically, the aforementioned physical vapor deposition process can be performed in a chamber where a shutter is positioned between the sputtering source and the target substrate. The shutter can be operated rapidly (i.e., opened and closed) to shield the target substrate from the sputtering source for a short period of time. Due to the rapid nature of the shutter, sensitive perovskite and transport layers may be damaged by ion bombardment and exposure to UV radiation. Furthermore, the entire target substrate is subjected to the entire sequence of TCO deposition, which can take several minutes to achieve a thickness of approximately 300–900 nm to meet sheet resistance and transport requirements. As such, the physical vapor deposition process can inherently cause greater ion and UV damage to the target substrate than expected, which can lead to defects and recombination sites in the layers of the target substrate, thereby degrading the electrical performance as an electron-hole pair absorber layer.

[0095] To overcome the disadvantages of conventional physical vapor deposition processes, the TCO layers (110 and 130) can instead be manufactured in an inline manufacturing process. The inline manufacturing process can be performed in multiple process chambers where the deposition of a selected target material takes place. A conveyor belt can transport the target substrate between the multiple process chambers. The inline manufacturing process can provide the deposition of the TCO layer while maintaining the low resistance, excellent transmittance, and uniform thickness of the perovskite solar cell. The inline manufacturing process can be a vertical or horizontal process. An example of a horizontal inline manufacturing system is shown in FIG. 14.

[0096] The inline manufacturing process can reduce defects formed in the ETL (125) and perovskite layer (120) by ultraviolet and argon / oxygen ions generated by the plasma in the TCO physical vapor deposition process. The use of a moving conveyor belt in a multi-process chamber can reduce defects formed in the ETL (125) and perovskite layer (120). A multi-chamber system can minimize the time the target substrate is exposed to plasma deposition. The target substrate may be exposed to deposition only in specific chambers. For example, the target substrate may not be exposed to deposition in a buffer chamber, whereas the target substrate is exposed to deposition in a process chamber where the first and second TCO layers are fabricated. In some embodiments, a target substrate comprising an upper glass plate (105), a first TCO layer (110), an HTL (115), a perovskite layer (120), and an ETL (125) is loaded onto a conveyor belt of an inline PVD manufacturing tool. A conveyor transports a target substrate to a target chamber so that the ETL layer (125) faces the TCO source for TCO deposition. Depending on the desired thickness and composition of the second TCO layer and the throughput of the TCO source, there may be one or multiple target substrates at a time inside the chamber, or multiple chambers with a single target substrate. Each chamber may be separated by a gate to minimize cross-contamination and damage from plasma exposure. In some cases, the target substrate passes through a first deposition chamber for the deposition of an ITO buffer layer. Then the substrate passes through a buffer chamber and finally through a second deposition chamber for the deposition of a bulk layer of ITO. The buffer chamber can prevent cross-contamination between the first deposition chamber and the second deposition chamber, for example, if the composition or deposition parameters of the two ITO layers are different.

[0097] To further reduce direct exposure to deposition, the moving target substrate on the conveyor belt ensures that only specific parts of the target substrate are directly exposed to deposition until the corresponding part of the target substrate moves past the deposition area. The duration of direct exposure of each part of the target substrate depends on the speed of the conveyor belt. The conveyor belt speed can be adjusted to ensure that each layer is sufficiently deposited on the target substrate while minimizing the direct exposure time of each part of the substrate. The moving conveyor belt provides a more gradual deposition profile on the target substrate, in contrast to the more abrupt profiles generated by conventional shutters.

[0098] Multiple chambers may also include shields or other blocking obstacles between chambers to block ion and UV exposure from other chambers when a target substrate enters a chamber without deposition. Multiple chambers may also include shields around the deposition area to block ion and UV radiation from substrate areas not directly exposed to deposition. Furthermore, the multiple chamber system allows for the deposition of TCO layers with uniform thickness and much lower plasma power without compromising the deposition time.

[0099] The inline manufacturing process may also implement the aforementioned techniques (e.g., optimization of process parameters such as gas flow / pressure, deposition power, thickness and material, use of a buffer layer, reduction of deposition energy, use of an ultrathin silver layer, and use of an annealing process) when fabricating the second TCO layer to further reduce defects formed in the ETL (125) and the perovskite layer (120). This process limits the number of defects at both the interface between the second TCO layer (130) and the ETL (125) and in the bulk of the ETL (125) and the perovskite layer (120). Other non-limiting examples of process parameters include chemical formation parameters (e.g., solvent composition, presence or absence of additives, 1-working formulation, 2-working formulation, etc.), ultrasonic atomization for process parameters (e.g., atomization volume, atomization speed, ultrasonic output, substrate lateral velocity, nozzle height, nozzle width, nozzle angle, environmental factors, humidity, atmospheric composition, temperature, etc.), post-application treatment parameters (e.g., drying period, rinsing period, external environmental parameters, solvent chemistry, annealing time, annealing temperature, etc.), transport layer application parameters (e.g., application type, surface condition, layer thickness, layer conformability, etc.), or any combination thereof.

[0100] FIG. 3 is a flowchart of a manufacturing process (300) for forming a perovskite photovoltaic cell. The process 300 may optionally include a step (310) of forming a substrate comprising a first transparent conductive layer and a hole transport layer. In some cases, a pre-formed substrate may be provided instead.

[0101] FIG. 4 is a flowchart of operation 310 of FIG. 3. Operation 310 may include the step (311) of providing a substrate. The substrate may be a transparent substrate. The substrate may comprise silicon-based glass (e.g., amorphous silicon dioxide, doped silicon dioxide, etc.), transparent conductive oxide, ceramic, chalcogenide glass, polymer (e.g., transparent plastic, poly(methyl methacrylate, etc.), etc.), or any combination thereof. The substrate may comprise the top surface of a photovoltaic module. For example, the substrate may be the top glass of a silicon photovoltaic panel assembly. The substrate may be textured and / or patterned. For example, the substrate may comprise nanoscale texturing configured as an anti-reflective coating and an adhesive surface. In another example, the substrate may comprise patterning configured to create a photonic channel. In yet another example, the substrate may comprise a patterned portion (e.g., top contact grid layout) having an electrode for removing energy from a solar cell. The substrate is at least about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, It can have an area of ​​14, 15, 20, or 25 square meters or more. The substrate can have an area of ​​up to approximately 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1 square meters or less. The substrate can be a large format substrate. For example, the substrate can be a 10th generation substrate.

[0102] Work 310 may include the step (312) of forming a first transparent conductive layer by applying one or more first transparent conductive materials to a substrate. The first transparent conductive layer may include a transparent conductive oxide (e.g., indium tin oxide (ITO), indium zinc oxide, aluminum zinc oxide, indium cadmium oxide, etc.), a transparent conductive polymer (e.g., poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), poly(4,4-dioctyl cyclopentadithiophene), etc.), carbon nanotubes, graphene, nanowires (e.g., silver nanowires), a metal grid (e.g., a grid contact containing metal), a thin film (e.g., a metal thin film), a conductive grain boundary, etc., or any combination thereof. The transparent conductive layer may have a total spectral transparency of at least about 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, and 99.9%. The transparent conductive layer may have a total spectral transparency of up to about 99.9%, 99%, 98%, 97%, 96%, 95%, 90%, 85%, 80%, 75%, 70%, 60%, 50%, 40%, 30%, and 20%. The transparent conductive layer may have a total spectral transparency within a range defined by any two of the aforementioned progression values. For example, the transparent conductive layer may have a total spectral transparency of 75% to 85%. The transparent conductive layer can have transparency of at least about 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, and 99.9% across the spectral band. The transparent conductive layer can have transparency of up to about 99.9%, 99%, 98%, 97%, 96%, 95%, 90%, 85%, 80%, 75%, 70%, 60%, 50%, 40%, 30%, and 20% across the spectral band.For example, the transparent conductive layer may have a transmittance of 85% over a wavelength range of 400 nm to 1200 nm. The transparent conductive layer may act as a barrier to the perovskite layer against moisture, gas, dust, etc. The transparent conductive layer may also prevent the diffusion of ions (e.g., metal ions) that may affect the performance of the perovskite layer. Methods for forming the transparent conductive oxide layer are described elsewhere in this specification. For example, the transparent conductive oxide layer may be formed using the PVD and / or in-line manufacturing processes described herein.

[0103] Operation 310 may include the step (313) of applying one or more hole transport layers to a transparent conductive layer. One or more hole transport layers may be configured to transport holes from the absorption layer to the transparent conductive layer and out of the photovoltaic module. One or more hole transport layers may be organic molecules (e.g., 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD)), inorganic oxides (e.g., nickel oxide (NiO₂)). x ) , Copper oxide (CuO x ) , Cobalt oxide (CoO₂) x ), chromium oxide (CrO x ), vanadium oxide (VO x ), Tungsten oxide (WO) x ), molybdenum oxide (MoO x ), copper aluminum oxide (CuAlO2) , Copper chromium oxide (CuCrO2) , Copper gallium oxide (CuGaO2) It may include inorganic chalcogenides (e.g., copper iodide (CuI), indium copper sulfide (CuInS2), copper zinc tin sulfide (CuZnSnS4), copper barium tin sulfide (CuBaSnS4), etc.), other inorganic materials (e.g., copper thiocyanate (CuSCN), etc.), organic polymers, etc., or combinations thereof. For example, a glass substrate covered with indium tin oxide may be coated with nickel oxide to form a hole transport layer on a transparent conductive layer.

[0104] Operation 310 may optionally include the step (314) of performing one or more lithography operations on the hole transport layer. The one or more lithography operations may include optical lithography (e.g., (extreme) ultraviolet lithography, X-ray lithography, laser scribing, etc.), electron beam lithography, ion beam lithography, nanoimprint lithography, other direct recording processes (e.g., dip-pen lithography, inkjet printing, etc.), or a combination thereof. For example, multiple features may be engraved on the hole transport layer using laser scribe. The one or more lithography operations may include adding and / or subtracting features. For example, features may be cured to make them permanent. In other examples, features may be formed by removing material from a target.

[0105] Returning to FIG. 3, process 300 may include a step (320) of applying one or more perovskite precursors to a hole transport layer. The application may be by chemical vapor deposition (CVD), plasma-enhanced CVD, atomic layer deposition, spin coating, dip coating, doctor blading, drop casting, centrifugal casting, chemical solution deposition, sol-gel deposition, plating, physical vapor deposition, thermal evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, cathode arc deposition, ultrasonic spraying, inkjet printing, etc., or a combination thereof. The application may include applying a single perovskite precursor at once. For example, a first perovskite precursor may be evaporated onto the hole transport layer, and then a second perovskite precursor may be sprayed onto the first precursor. The application may include applying multiple precursors at once. For example, an inkjet printer may apply a solution containing multiple precursors. Process 300 may optionally include the step (330) of applying one or more additional perovskite precursors to the hole transport layer. The additional perovskite layer may be applied in the same manner as in process 320. For example, a first precursor may be deposited by physical vapor deposition, and then a second precursor may be deposited by physical vapor deposition. Alternatively, the additional perovskite layer may be applied in a manner different from that of process 320. For example, the first perovskite precursor may be deposited by physical vapor deposition, and the second perovskite precursor may be deposited by ultrasonic spraying. Process 330 may be repeated multiple times. For example, multiple additional perovskite precursors may be applied to the hole transport layer in multiple processes.

[0106] Ultrasonic atomization applications may involve the use of multiple atomization nozzles. The ultrasonic atomization process may involve the use of a single atomization nozzle. For example, a single atomization nozzle may be configured to raster across an application area to provide coverage of that area. Multiple different types of atomization nozzles may be tested for the formation of a film of a certain uniformity and / or thickness deposited by the atomization nozzle, and the optimal atomization nozzle may be selected from among the multiple different types of atomization nozzles. Once the optimal atomization nozzle is selected, multiple nozzles of that type may be used for ultrasonic atomization applications. Multiple nozzles may form a nozzle bank configured to atomize over a wide area to improve throughput and efficiency. The nozzle bank may be a nozzle strip (e.g., a line of nozzles over a single dimension), a two-dimensional array of nozzles (e.g., nozzles distributed over a rectangular shape), or a three-dimensional array of nozzles (e.g., multiple nozzles distributed in three dimensions). The atomization nozzles may be adjusted to spray obliquely at any angle. The angle may be spaced at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 degrees or more from a line parallel to the substrate. The angle may be offset from a line parallel to the substrate by up to approximately 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 degree. The angle may be configured to reduce or remove precursors that miss the substrate and contaminate other components of the manufacturing process. Using ultrasonic atomization applications enables a roll-to-roll inline fabrication process.In a roll-to-roll inline manufacturing process, a series of nozzle banks can sequentially add different layers to a substrate, process the substrate (e.g., annealing, laser scribing), and produce a finished photovoltaic cell on a single line. Using a roll-to-roll process can significantly improve cost and production speed compared to a step-by-step manufacturing process.

[0107] One or more perovskite precursors may include one or more lead halides (e.g., lead fluoride, lead chloride, lead bromide, lead iodide, etc.), lead salts (e.g., lead acetate, lead oxide, etc.), other metal salts (e.g., manganese halide, tin halide, metal oxide, metal halide, etc.), organic halides (e.g., formamidinium chloride, formamidinium bromide, formamidinium iodide, methylammonium chloride, methylammonium bromide, methylammonium iodide, butylammonium halide, etc.), alkali metal salts (e.g., alkali metal halides, etc.), alkaline earth metal salts (e.g., alkaline earth metal halides, etc.), perovskite nanoparticles, etc., or any combination thereof. Multiple perovskite precursors may be used as one or more perovskite precursors. For example, both methylammonium iodide and butylammonium iodide can be used as perovskite precursors. In this example, the ratio of methylammonium iodide to butylammonium iodide used can be approximately 1:99, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 10:90, or 99:1. In another example, a mixture of lead halides can be used as part of the perovskite precursor. Using different mixtures of lead halides can adjust the band gap of the perovskite layer. For example, using different mixtures of lead bromide (II) and lead iodide (II) can result in different band gaps. Using different amounts of lead chloride (II) can affect the crystal stability of the perovskite layer and prevent phase separation within the layer. The amount of added lead chloride (II) may be greater than the amount of added lead bromide (II) by weight. The amount of added lead chloride (II) may be less than the amount of added lead bromide (II) by weight. The amount of added lead chloride (II) may be equal to the weight of added lead bromide (II).The amount of lead iodide (II) dissolved in the solution may be related to the amount of lead bromide (II) and lead chloride (II) in the solution. For example, if more lead bromide (II) and lead chloride (II) are added to the lead iodide (II) solution, the solubility of lead iodide (II) is improved and the fine particles of the perovskite layer may be reduced.

[0108] One or more perovskite precursors may be one or more perovskite precursor solutions. For example, a lead iodide (II) solution of dimethyl sulfoxide may be a perovskite precursor. The perovskite precursor may be a perovskite precursor solution containing at least about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99 weight percent or more. The perovskite precursor may be a perovskite precursor solution in an amount of up to about 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, or 0.1 weight percent or less. The solution may contain one or more solvents. Examples of solvents may be polar solvents (e.g., water, dimethyl sulfoxide, dimethylformamide, ether, ester, acetate, acetone, etc.), nonpolar solvents (e.g., hexane, toluene, etc.), etc., or combinations thereof. The proper mixing of solvents and solvent compositions can contribute to controlling the solvent removal rate, thereby influencing grain development and bulk defect formation. By adjusting the interaction between the solvent coordination strength and the evaporation rate of the precursor solution, the reaction kinetics of the formed perovskite film can be better controlled. For example, a fast-evaporating, weak coordination solvent may form a more disordered film, but it may also result in less residual solvent present in the film. Solvent mixtures can perform functions such as improving solute solubility, reducing evaporation rates, and enhancing the performance of application methods. For instance, a combination of NMP and DMSO can increase solute solubility and decrease the solvent evaporation rate.In this example, the characteristics of the NMO / DMSO mixture can reduce the premature crystallization of the perovskite and improve film quality. In another example, adding NMP to DMF can increase the spray width of the solution through ultrasonic spraying on the device, which can provide greater flexibility in the spray parameters used.

[0109] One or more perovskite precursors may comprise one or more additives. The addition of one or more additives may be configured to reduce and / or eliminate defects within the perovskite layer as prepared elsewhere in this specification. One or more additives may comprise one or more recrystallization solvents. One or more recrystallization solvents may be added to a solution containing one or more perovskite precursors. One or more recrystallization solvents may be applied after the deposition of one or more perovskite precursors and / or after the annealing of one or more perovskite precursors. For example, a lead halide precursor may be applied and then a recrystallization solvent may be applied, and the perovskite precursor may be further annealed to orient the lead halide precursor for better methylammonium iodide integration. Non-limiting examples of recrystallization solvents include halobenzene (e.g., chlorobenzene, bromobenzene, etc.), haloform (e.g., chloroform, iodoform, etc.), ether (e.g., diethyl ether), or combinations thereof.

[0110] Various parameters can be adjusted to provide a desired perovskite layer. Examples of parameters include the temperature of the perovskite precursor solution application, the volumetric application rate, the ultrasonic power of the ultrasonic spray element, the lateral velocity of the precursor application (e.g., the speed of the substrate moving through the applicator), the applicator height (e.g., the distance from the applicator to the substrate), environmental factors (e.g., humidity, reactive gas content, temperature, etc.), the wetting surface energy, etc., or any combination thereof. Any part of process 300 comprising the application of the perovskite precursor may take place in a controlled environment. The controlled environment may have a relative humidity of at least about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 99%. The controlled environment may have a relative humidity of up to about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, or 10%. It may. The controlled environment may include a controlled atmosphere. The controlled atmosphere may include an inert gas (e.g., nitrogen, noble gas, etc.). The controlled atmosphere may have an oxygen content of at least about 1 part per million (ppm), 10 ppm, 50 ppm, 100 ppm, 500 ppm, 1,000 ppm, 5,000 ppm, 1%, 5%, 10%, 15%, 20% or more. The controlled atmosphere may have an oxygen content of up to about 20%, 15%, 10%, 5%, 1%, 5,000 ppm, 1,000 ppm, 500 ppm, 100 ppm, 50 ppm, 10 ppm, 1 ppm or less. The controlled atmosphere may have at least about 15, 20, 25, 30, 35, 40, It can have a temperature of 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200℃ or higher.The controlled atmosphere may have a temperature of up to approximately 200, 190, 180, 170, 160, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15℃ or lower.

[0111] Process 300 may include a step (340) of performing one or more processing operations on a perovskite precursor to produce a perovskite layer. If the perovskite precursor is deposited instead of the finished perovskite layer, operation 340 may be omitted. FIG. 5 is a flowchart of operation 340 of FIG. 3. Operation 340 may include a step (341) of providing a substrate comprising a first transparent conductive layer, a hole transport layer, and one or more applied perovskite precursors. The substrate may be the result of operations 310-330 of process 300.

[0112] Operation 340 may include the step (342) of performing one or more processing operations on a perovskite precursor to produce a perovskite layer. One or more processing operations may include annealing, light exposure (e.g., UV exposure), stirring (e.g., vibration), functionalization (e.g., surface functionalization), electroplating, template inversion, etc., or any combination thereof. For example, a substrate having a perovskite precursor may be annealed to form a perovskite layer from the precursor. In other examples, the perovskite precursor may be annealed and subsequently functionalized. The annealing may be annealed under an inert atmosphere (e.g., an argon atmosphere, a nitrogen atmosphere). The annealing may be performed under a reactive atmosphere (e.g., an atmosphere containing a reagent (e.g., methylammonium). Annealing can be performed at a temperature of at least about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200°C or higher. Annealing may be performed at temperatures up to approximately 200, 190, 180, 170, 160, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, and 15°C. Annealing may be performed within a temperature range defined by any two of the aforementioned values. For example, annealing may be performed at a temperature of 90 to 120 degrees Celsius. Annealing can be performed for at least about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 75, 90, 105, 120 minutes or more.Annealing may be performed for a maximum of approximately 120, 105, 75, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.5 minutes. Annealing may be performed for a period defined by any two of the aforementioned values. For example, annealing may be for approximately 5 minutes to approximately 15 minutes. Multiple annealing processes may be applied to the substrate. For example, the substrate may be annealed at a first time and temperature, and then annealed again at a second time and temperature. These additional annealing processes can reduce the number of defects present in the perovskite layer and improve performance.

[0113] Operation 340 may include the step (343) of applying one or more additional layers to the perovskite layer. The one or more additional layers may include one or more additional perovskite layers. For example, a second perovskite layer having a different band gap may be applied to the first perovskite layer. The one or more additional layers may include one or more additional perovskite precursors. For example, iodine gas may be applied to form an iodine layer on the perovskite layer and / or the perovskite precursor layer. The one or more additional layers may include one or more washing operations. The washing operations may include applying a solvent to the perovskite layer. Examples of solvents include, but are not limited to, water, non-polar organic solvents (e.g., hexane, toluene, etc.), polar organic solvents (e.g., methanol, ethanol, isopropanol, acetone, etc.), ionic solvents, etc. One or more additional layers may comprise one or more passivation layers. The passivation layers may comprise reagents configured to passivate and / or stabilize the perovskite layer. For example, the application of a solution containing phenethylammonium iodide may passivate and stabilize the particles of the perovskite layer.

[0114] Operation 340 may include the step (344) of performing one or more lithography operations on one or more additional layers and / or perovskite layers. The one or more lithography operations may be one or more lithography operations as described elsewhere in this specification. For example, a shape may be created on the perovskite layer using a laser scribe.

[0115] Returning to FIG. 3, process 300 may include the step (350) of applying an electron transport layer to a perovskite layer. FIG. 6 is a flowchart of process 350 of FIG. 3. Process 350 may include the step (351) of providing a substrate comprising a first transparent conductive layer, a hole transport layer, and a perovskite layer. The substrate may be the substrate produced by processes 310-340 of FIG. 3.

[0116] Work 350 may include the step (352) of applying an electron transport layer to a perovskite layer. The electron transport layer may be applied by methods and systems as described in other parts of this specification (e.g., physical vapor deposition, ultrasonic spraying, etc.). The electron transport layer may comprise a material having a conduction band minimum value smaller than that of the perovskite layer. For example, if the perovskite layer has a conduction band of at least -3.9 eV, the electron transport layer may have a conduction band of at least -4 eV. Examples of electron transport layer materials include, but are not limited to, titanium oxide (e.g., TiO2), zinc oxide, tin oxide, tungsten oxide, indium oxide, niobium oxide, iron oxide, cerium oxide, strontium titanium oxide, zinc tin oxide, barium tin oxide, cadmium selenide, indium sulfide, lead iodide, organic molecules (e.g., phenyl-C61-butyric acid methyl ester (PCBM), poly(3-hexylthiophene-2,5-diyl) (P3HT), etc.), lithium fluoride, buckminsterfullerene (C60), etc., or combinations thereof. Operation 350 may optionally include the step (353) of performing one or more lithographic operations on the electron transport layer. The one or more lithographic operations may be one or more lithographic operations as described elsewhere in this specification. For example, a laser scribe may be used to create features on the electron transport layer.

[0117] Returning to FIG. 3, process 300 may include the step (360) of applying a second transparent conductive layer to an electron transport layer. FIG. 7 is a flowchart of operation 360 of FIG. 3. Operation 360 may include the step (371) of providing a substrate comprising a first transparent conductive layer, a hole transport layer, a perovskite layer, and an electron transport layer. The substrate may be the substrate produced by operations 310-350 of FIG. 3.

[0118] Operation 360 may include the step (362) of applying a second transparent conductive layer to the electron transport layer. The second transparent conductive layer may be of the same type as the first transparent conductive layer. For example, both the first and second transparent conductive layers may be indium tin oxide. The second transparent conductive layer may be of a different type from the first transparent conductive layer. The second transparent conductive layer may be deposited as described elsewhere in this specification (e.g., physical vapor deposition, etc.).

[0119] Operation 360 may include the step (363) of applying one or more busbars to the second transparent conductive layer. One or more busbars may be applied as busbars (e.g., a pre-formed busbar may be applied to the second transparent conductive layer). For example, a mask may be used to form the busbars in an evaporation process. One or more busbars may be applied as solid films and subsequently formed into busbars. For example, a silver film may be deposited on the second transparent conductive layer and etched to form the busbars. In another example, a laser scribe may be used to form the busbars from a silver film. Operation 360 may optionally include the step (364) of performing one or more lithography operations on the electron transport layer. The one or more lithography operations may be one or more lithography operations as described elsewhere in this specification. For example, a laser scribe may be used to create features on the second transparent conductive layer. The busbars may be attached to at least about two, three, or four terminals. The busbar can be attached to up to about 4, 3, or 2 terminals. The terminals can be configured to form a parallel connection with one or more additional photovoltaic modules. The terminals can be configured to form a series connection with one or more additional photovoltaic modules. The terminals can be scribed (e.g., laser scribed). The terminals can be configured to enable the connection of a perovskite photovoltaic device and another photovoltaic device before the lamination of two photovoltaic devices. For example, the perovskite photovoltaic device can be connected to a silicon photovoltaic device through two terminals.

[0120] Returning to FIG. 3, process 300 may include the step (370) of applying an encapsulant to the second transparent conductive layer. The encapsulant may be configured to reduce or substantially eliminate the exposure of the perovskite layer to one or more reactive species. Examples of reactive species include, but are not limited to, oxygen, water, and polar molecules (e.g., polar volatile organic compounds, acids, etc.). The encapsulant may be substantially transparent. For example, the encapsulant may be transparent in the same light region as the transparent conductive layer. Non-limiting examples of the encapsulant may include polymers (e.g., butyl rubber, poly(methyl methacrylate), polycarbonate, polyethylene, polystyrene, thermoplastic olefin, polypropylene, etc.), waxes (e.g., paraffin wax), metals (e.g., iron, copper), semiconductors (e.g., wide bandgap semiconductors (e.g., zinc oxide, titanium oxide)), or any combination thereof.

[0121] The encapsulant may be applied over the second transparent conductive layer (e.g., applied to the entire layer), a portion of the second transparent conductive layer (e.g., a portion of the layer), up to the edges of the second transparent conductive layer (e.g., as a seal for the entire stack of layers), or any combination thereof. For example, the encapsulant may be applied to the edges of the entire layer stack to prevent moisture and oxygen diffusion into the stack. The encapsulant may be applied to the first conductive layer as well as the second conductive layer. For example, the substrate may include the encapsulant between the substrate and the first conductive layer. Example 3 described below describes the use of PDMS as the encapsulant. Other examples of encapsulants include HelioSeal TMExamples include, but not limited to, silicone adhesives, butyl sealants, etc. For edge encapsulation, the encapsulating material may include tape. The tape may be an adhesive barrier. The encapsulating material may be positioned to end at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 millimeters from the edge. The bag material can be arranged to end at a maximum of about 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 millimeter or less from the edge.

[0122] Following Work 370, the completed stack (e.g., substrate, perovskite layer, and other layers) can be used as a front panel for an additional photovoltaic module. For example, the completed stack can be configured as a front junction of a 2-junction photovoltaic module. The completed stack can be configured to be used as a substrate for an additional stack. For example, the stack can be used as an initial substrate for growing a silicon photovoltaic module. The stack can be stacked on a second photovoltaic module. The stack can be laminated at a temperature of at least about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200℃ or higher. The stack can be laminated at a maximum temperature of approximately 200, 190, 180, 170, 160, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15℃.

[0123] FIG. 13 is a flowchart of a fabrication process 1300 for forming a perovskite layer. Process 1300 may be an embodiment of operations 320-340 of FIG. 3. Process 1300 may include the step (1310) of providing a substrate comprising a hole transport layer. The substrate may also comprise a transparent conductive layer as described elsewhere in this specification. The hole transport layer may be a hole transport layer as described elsewhere in this specification. The substrate may be a substrate as described elsewhere in this specification.

[0124] Process 1300 may include the step (1320) of applying a lead layer to the hole transport layer. The lead layer may comprise lead metal (e.g., lead (0)), lead salts (e.g., lead acetate (II), lead halide (II), lead (I) salts, etc.), or a combination thereof. For example, a metallic lead layer may be deposited on the hole transport layer, and a lead acetate (II) layer may be applied to the lead layer. The lead layer may be deposited as described elsewhere in this specification. For example, the lead may be deposited by physical vapor deposition. The lead layer may be deposited by the same deposition method and / or deposition machine as the hole transport layer. For example, both the hole transport layer and the lead layer may be deposited using the same physical vapor deposition equipment.

[0125] Process 1300 may include the step (1330) of applying an organic halide salt layer to a lead layer. The organic halide may be an organic halide as described elsewhere in this specification. For example, a mixture of methylammonium iodide, methylammonium chloride, and formamidinium iodide may be applied to the lead layer. The organic halide layer may be applied by a deposition process as described elsewhere in this specification. For example, the organic halide may be applied by a spin coating process, an ultrasonic spraying process, etc.

[0126] Process 1300 may include the step (1340) of applying a halide layer to an organic halide layer. The halide layer may comprise a halide (e.g., fluorine, chlorine, bromine, iodine, etc.), an oxyhalide (e.g., chlorate, etc.), other halide-containing compounds, etc., or any combination thereof. For example, the halide layer may comprise iodine. In other examples, the halide layer may be iodine. The halide layer may be applied to the organic halide salt layer by a deposition process described elsewhere in this specification. The halide may be applied as a gas. For example, iodine may be sublimated and applied as a gas to the organic halide salt layer. The halide may be applied uniformly over the entire surface of the organic halide salt layer. Various application devices may be used to apply the halide uniformly. An example of an application device may be a 'shower head' (e.g., an application head comprising a plurality of holes). An example of a shower head for the application of a perovskite precursor can be found in Fig. 9. Another example of an application device may be a rod comprising one or more nozzles capable of moving across the surface of a substrate. For example, a rod of the same width as the substrate may move across the substrate to deposit a uniform halide coating.

[0127] Process 1300 may include a step (1350) of performing one or more processing operations to form a perovskite layer. The perovskite layer may be a perovskite layer as described elsewhere in this specification (e.g., the perovskite layer of FIG. 3). The one or more processing operations may be one or more processing operations as described elsewhere in this specification. For example, a lead layer with a lead acetate layer deposited thereon, a methylammonium iodide / formamidinium iodide layer, and an iodide layer may be annealed together at a temperature of 90 to 120 degrees Celsius to form a methylammonium / formamidinium iodide perovskite layer. One or more processing operations may include washing. Washing may include the use of one or more solvents described elsewhere in this invention. Washing may be configured to remove unreacted precursors from the perovskite layer. For example, isopropanol may be used to remove residual organic halide salts. One or more treatment operations may include one or more treatments. Examples of treatments include, but are not limited to, the application of phenethylammonium iodide, thiocyanate washing, other passivation and / or stabilization processes, or any combination thereof.

[0128] In another aspect, the present invention provides a method for producing a perovskite layer comprising spraying a solution containing a precursor for a perovskite layer. A quenching solution may be applied to the precursor to form a perovskite layer. The solution may contain any precursor for a perovskite layer. For example, the solution may contain lead halides, organic halides, and halides. The solution may contain perovskite precursors as described elsewhere in this specification. The solution may be applied by a process described elsewhere in this document. For example, the solution may be applied by ultrasonic spraying as described in the technique. The solution may be treated after application. For example, the solvent may be removed from the solution by heating the solution. The solution may not be treated after application. The quenching solution may be applied to the solution (e.g., the precursor solution). The quenching solution may be applied to the dried precursor. The quenching solution may contain an antisolvent (e.g., a solvent in which the perovskite precursor is less soluble than the solvent for the precursor solution). Non-limiting examples of antisolvents include polar solvents (e.g., alcohol, acetone, etc.), long-chain nonpolar solvents (e.g., octadecene, squalene, etc.), or any combination thereof. The quenching solution may be applied as described elsewhere in this invention. For example, the quenching solution may be applied by ultrasonic spraying technology. The solution may be placed under one or more atmospheric conditions to aid in solvent removal. One or more atmospheric conditions may include reduced pressure (e.g., application of vacuum), increased pressure (e.g., blowing gas over the substrate), or a combination thereof. Reduced pressure may include the application of a partial vacuum around the substrate. Such a vacuum may perform rapid solvent removal and draw solvent from the film to produce a high-quality film. Increased pressure may include the use of an air knife or a similar blowing method to aid in solvent removal.These high-quality films may be visible reflectively in visual inspection. After applying the precursor solution, the solution may be given time to level itself before solidifying. For example, the precursor solution may be allowed to lie on the substrate for a sufficient amount of time before removing the solvent and preparing the perovskite layer.

[0129] FIG. 8 schematically illustrates a perovskite precursor deposition chamber. Gas may flow from an inlet (801) into a chamber (802). The gas may be an inert gas (e.g., nitrogen, argon, etc.). The chamber (802) may contain one or more perovskite precursors. For example, the chamber may contain solid iodine. In other examples, the chamber may contain liquid bromine. The gas may consist of a carrier gas for one or more perovskite precursors in a reservoir. For example, the gas may carry sublimated iodine out of the chamber. The chamber may contain an optical sensor assembly (803). The optical sensor assembly may include a light source and a detector as described elsewhere in this specification. For example, the optical sensor assembly may include a green laser and a photodiode detector. The gas may pick up one or more perovskite precursors from the chamber (802) and flow into a chamber (804). The chamber (804) may be configured to control the flow of gas and / or one or more perovskite precursors from the chamber (802). The chamber is configured to prevent leakage from the deposition chamber (806). The chamber (804) may be configured with a bubbler (e.g., water bubbler, mercury bubbler, etc.), a mass flow controller (e.g., iodine mass flow controller, etc.), etc., or a combination thereof. Gas may flow from the chamber (804) to the chamber (806) through an additional optical sensor assembly (805). The optical sensor assembly (805) may include a light source and a detector as described elsewhere in this specification. For example, the optical sensor assembly may include a green laser and a photodiode detector. The chamber may be a chamber as described elsewhere in this specification. For example, the chamber may be a chamber as described in FIG. 9. The chamber (808) may be made of or coated with a material resistant to halide gas.For example, the chamber may be made of titanium. In another example, the chamber may include an inert polymer coating. In another example, the chamber is made of glass. The chamber may be connected to an exhaust port (807), and the exhaust port may be connected to the chamber (808). The chamber (808) may include a bubbler. The chamber (808) may include a condenser element (e.g., a cold head, a cold finer, a cold coil, etc.). The chamber (808) may be configured to prevent one or more perovskite precursors from flowing out of the chamber (806) and into the downstream environment. For example, the cold head may condense iodine gas to prevent it from being released into the atmosphere.

[0130] FIG. 9 schematically illustrates a shower head design for a spray nozzle. Gas can flow through an inlet (901) to a deposition chamber (903) through a nozzle (902). The nozzle (902) may include a plurality of holes (904). The plurality of holes may be at least about 2, 5, 10, 25, 50, 75, 100, 150, 200, 250, 500, 750, 1,000 or more holes. The plurality of holes may be up to about 1,000, 750, 500, 250, 200, 150, 100, 75, 50, 25, 10, 5, or 3 or fewer holes. The plurality of holes may be configured to evenly distribute gas from the inlet (901) onto a substrate (905) inside the chamber (903). The substrate may be a substrate as described elsewhere in this specification. The substrate may be placed on a heater (906). The heater may be configured to anneale the substrate. For example, the heater may anneale the substrate so that a perovskite precursor reacts to form a perovskite layer. The chamber (903) may include one or more exhaust ports (907). The exhaust ports may be configured to remove excess gas (e.g., excess reactants, oxygen, water, etc.) from the atmosphere of the chamber. The chamber may include a light source (908) directed toward a photodetector (909). The light source may include a laser (e.g., a green laser), an incoherent light source (e.g., a light-emitting diode), or a combination thereof. The photodetector may be a zero-dimensional (0D) detector (e.g., ,It may include a photodiode), a one-dimensional (1D) detector (e.g., a strip detector), a two-dimensional (2D) detector (e.g., an array detector), a film detector (e.g., a detector using silver halide crystals in a film), a phosphorescent material plate detector (e.g., a downshifting or down-converting phosphorescent material plate), a semiconductor detector (e.g., a semiconductor charge-coupled device (CCD), a CMOS (complementary metal oxide semiconductor) device), or any combination thereof. The substrate may be loaded into an oven for an annealing process. For example, the substrate may be loaded into the oven along with a plurality of other substrates via an automated loader to perform a batch annealing process.

[0131] FIG. 20 is a flowchart of process 2000 for manufacturing a tandem photovoltaic module according to some embodiment of the present disclosure. The method may include the step (2010) of providing a silicon photovoltaic panel. The silicon photovoltaic panel may be as described elsewhere in this specification. For example, the silicon photovoltaic panel may be a front contact photovoltaic panel, an integrated rear contact photovoltaic panel, a shingled photovoltaic panel, etc. The silicon photovoltaic panel may have at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 72, 75, 80, 85, 90, 95, 96 or more solar cells. A silicon solar panel may have up to approximately 96, 95, 90, 85, 80, 75, 72, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, and 10 or fewer solar cells. In some embodiments, the silicon solar panel has 60 6-inch solar cells arranged in a 6×10 grid. The cells may be connected in series. Each cell may have an open-circuit voltage of 0.7 V for a total open-circuit voltage of approximately 42 V.

[0132] This method may further include the step (2020) of manufacturing a perovskite-on-glass as described elsewhere in this specification. The perovskite-on-glass may have at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more layers. The perovskite-on-glass may have up to about 10, 9, 8, 7, 6, 5, 4, 3, or 2 layers.

[0133] This method may further include the step (2030) of laser-scribing perovskite-on-glass to form a perovskite cell or strip. Such manufacturing may involve the use of manufacturing techniques as described elsewhere in this specification. For example, manufacturing may include using laser scribing to define one or more perovskite solar cells. The one or more perovskite solar cells may be a plurality of perovskite solar cells. One or more perovskite solar cells may be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99 or more perovskite solar cells. One or more perovskite solar cells may be up to approximately 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, and 2 or fewer perovskite solar cells. Multiple perovskite solar cells may be connected in series. Multiple perovskite solar cells may be connected in parallel. Laser scribing may separate the perovskite layer into multiple segments. Multiple segments may be formed from multiple perovskite solar cells. For example, contact may be applied to multiple segments to extract charge from multiple segments.

[0134] Laser scribing can be configured to produce multiple perovskite cells having the same or substantially the same voltage output as a silicon module when connected together. The voltage output of the perovskite layer per unit area can be known, and the perovskite layer can be scribed to form a perovskite cell of a size capable of providing a predetermined voltage. For example, the perovskite layer can be scribed to form five perovskite submodules each containing 40 perovskite solar cells to match a silicon photovoltaic module having the same voltage output as 40 perovskite solar cells each. In this example, the five perovskite submodules can be connected in parallel to increase the current generated in the perovskite layer while maintaining voltage matching with the silicon module.

[0135] This method may further include the step (2040) of connecting cells of a silicon solar panel to a perovskite solar cell to form a tandem module. The silicon solar panel and the perovskite solar cell may be in a voltage-matched configuration. The voltage-matched configuration may be as described elsewhere in this specification. For example, the silicon solar cell may have the same voltage as the perovskite solar cell. The perovskite solar cells may be connected in parallel with each other. The perovskite solar cells may be connected in series with each other. The perovskite solar cells may be connected such that there are multiple modules in the perovskite layer. For example, rows of perovskite solar cells may each be connected in series, and connected rows may be connected in parallel. The silicon solar panel and the perovskite solar panel may be connected as described elsewhere in this specification. For example, perovskite solar cells can be connected to the same junction box as silicon solar cells through copper (or other metals, charge collection tapes, etc.) terminals.

[0136] This method may further include the step (2050) of encapsulating the module. Encapsulation may include applying an encapsulating material as described elsewhere in the present invention. For example, encapsulation may include applying a thermoplastic polyolefin to a perovskite layer. In other examples, encapsulation may include the use of a transparent conductive oxide.

[0137] This method may include the step of applying a plurality of contacts to one or more perovskite solar cells to electrically connect one or more perovskite solar cells. The plurality of contacts may be applied using one or more processes as described elsewhere in this specification. For example, the plurality of contacts may be deposited onto the perovskite solar cells. In another example, the plurality of contacts may be applied to the perovskite solar cells by lithography. The method may include the step of applying an encapsulant to one or more perovskite solar cells. The application may be as described elsewhere in this specification. For example, the encapsulant may be applied via evaporation. In another example, the encapsulant may be spread as a viscous solution onto the perovskite solar cells. The encapsulant may be as described elsewhere in this specification. For example, the encapsulant may be a thermoplastic polyolefin. The method may include applying an edge sealant to one or more perovskite solar cells. The edge sealant may be the same as described elsewhere in this application. For example, the edge sealant is HelioSeal TM It could be.

[0138] Silicon solar panels and perovskite solar panels can be electronically coupled to the same junction box. This coupling to the same junction box allows the perovskite layer to be simply integrated into existing silicon solar modules. This coupling can also provide simple installation of tandem solar modules, as there can be a single output from the tandem module instead of multiple outputs.

[0139] FIGS. 16-19 show examples of various electrical network connections for various types of silicon-perovskite hybrid solar modules. Hybrid silicon-perovskite solar modules may be described elsewhere in this specification. FIG. 16 illustrates examples of the front and rear of silicon solar modules (1601 and 1602) as well as a perovskite top module (1603). The silicon solar module may include a front busbar (1604). The front busbar may be configured to connect various solar cells. The silicon solar module may include a terminal (1606). The terminal may include copper, silver, gold, iron, alloys thereof, charge collection tape, etc., or a combination thereof. The terminal may be configured to be electrically connected to the perovskite top module (1603). For example, the terminal may be configured to electrically connect the perovskite top module to a junction box. The terminal may be configured to provide a parallel connection between the silicon photovoltaic module and the perovskite top module. Alternatively, the terminal may be configured to provide a series connection between the silicon photovoltaic module and the perovskite top module. The tandem photovoltaic module may include a silicon photovoltaic panel. The silicon photovoltaic panel may include a plurality of silicon solar cells. The silicon photovoltaic panel may include a top glass plate. A plurality of silicon photovoltaic panels may be connected in series and may have a first open-circuit voltage. The tandem photovoltaic module may include a perovskite photovoltaic panel disposed on the underside of the top glass plate of the silicon photovoltaic panel. The perovskite photovoltaic panel may include a plurality of segments. Each of the plurality of segments may include a laser-scribe strip of a plurality of perovskites. The laser-scribe strips of a plurality of perovskites within the segment may be connected in series to generate a second open-circuit voltage that may be substantially equal to the first open-circuit voltage.A tandem solar module may include an interconnection that connects multiple segments of a plurality of silicon solar cells and a plurality of perovskite solar panels in parallel.

[0140] A plurality of segments may include at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 125, 150, 175, 200, 250, 300, 400, 500 or more segments. A plurality of segments may include up to approximately 500, 400, 300, 250, 200, 175, 150, 125, 100, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, and 2 or fewer segments. A plurality of segments may include a plurality of segments within a range defined by any two values ​​mentioned above. For example, a plurality of segments may include approximately 10 to approximately 200 segments.

[0141] The perovskite top module may include one or more channels (1607) and one or more terminals (1608). The channels may be created by methods described elsewhere in this specification. For example, the channels may be cut using a laser scribe. The channels may be configured to isolate different perovskite solar cells. In this way, a plurality of perovskite solar cells may be formed in the perovskite top module. A solar cell grid may be formed using additional channels perpendicular to the channels. For example, a 5 x 40 array of perovskite solar cell panels may be formed in the perovskite layer. The perovskite top module may include at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or more perovskite solar cells. The perovskite top module may include up to approximately 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, and 2 or fewer perovskite solar cells. For example, the perovskite top layer may include 40 solar cells separated by channels. The width of the perovskite solar cell may be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50 millimeters. The width of the perovskite solar cell may be up to about 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 millimeters.The length of the perovskite solar cell can be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 150, 200, 250, 500, 750, 1,000 millimeters or more. The length of the perovskite solar cell may be up to about 1,000, 750, 500, 250, 200, 150, 100, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 millimeters or less. The perovskite solar cell may be a strip (e.g., a solar cell that extends to the length of a module). The strips may be connected in series or in parallel. In some cases, the perovskite solar cells may be connected in series with each other. The perovskite solar cells may be connected in parallel with each other. Likewise, FIG. 17 illustrates an example of a stacked tandem perovskite-silicon photovoltaic module. The silicon photovoltaic panel may be a top contact photovoltaic panel. For example, the silicon photovoltaic panel may include electrical contacts configured to extract electricity from a panel located on the side of the silicon photovoltaic cell facing the sun. The module may include one or more encapsulating layers (1701). The one or more encapsulating layers may be as described elsewhere in this specification. One or more encapsulating layers may be applied to a substrate, and then the solar cells of the silicon photovoltaic module may be arranged on one or more encapsulating layers. Additional layers of encapsulating material may be applied over the silicon photovoltaic cells, and perovskite-on-glass may be applied to the encapsulating layers. The encapsulating layers may be configured to allow an electrical connection between the silicon layer and the perovskite layer.FIG. 18 illustrates an example of a perovskite top module electrically connected to an integrated back contact (IBC) silicon solar module. The silicon solar panel may be an integrated back contact solar panel. For example, the silicon solar panel may include electrical contacts configured to extract electricity from a panel located on the back of the silicon solar cell. FIG. 19 illustrates an example of a perovskite top module electrically connected to a shingled silicon solar module. The silicon solar panel may be a shingled solar panel. For example, multiple silicon solar cells may be stacked so that the back contact of one solar cell contracts with the front contact of an adjacent solar cell. In this example, the silicon solar cells may overlap only partially to provide a larger active area of ​​the solar panel.

[0142] Any size of the perovskite solar cell allows for any selection of the voltage output of the perovskite top module. For example, the perovskite solar cell can be configured to generate a predetermined voltage when the cell is illuminated. The perovskite solar cell can be configured to generate a total voltage substantially matching that of a silicon solar cell module. For example, in the case of a silicon solar cell with a 42-volt output, the perovskite solar cell can be configured to generate 44 volts. The perovskite top module can generate a voltage of at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 99% of the silicon solar cell module voltage. Perovskite top modules can generate voltages up to approximately 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, and 5% of the silicon solar module voltage. Voltage matching can be achieved between the two modules by matching the voltage of the perovskite top module with that of the silicon solar module, or by substation matching. Voltage matching conditions can produce hybrid modules with higher current output than non-voltage-matched hybrid modules. Silicon solar panels and perovskite solar panels can have nearly the same surface area. For example, the perovskite layer can cover the entire silicon solar panel. In this example, the total power of the module can be maximized by utilizing the entire area of ​​available sunlight. Perovskite solar panels may account for at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 99% of the silicon solar panel area. Perovskite solar panels may account for up to about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, and 5% of the silicon solar panel area. Perovskite composition and additives

[0143] The perovskite layer described in this specification is MA n1 FA n2 Cs n3 PbX3's It may have a composition, wherein MA is methylammonium and FA is formamidinium. n1, n2, and n3 may independently be greater than 0 and / or less than 1. n1 + n2 + n3 may be 1. A perovskite solar cell comprising the perovskite layer may maintain a photovoltaic conversion efficiency of at least about 80% after being irradiated for 300 hours under one solar condition in an air atmosphere at 45°C. The perovskite layer may be used as described elsewhere in this specification (e.g., as an absorption layer for a perovskite photovoltaic cell).

[0144] In the above formula, X may be selected from the group consisting of fluorine, chlorine, bromine, and iodine. For example, X may be iodine. X may be a combination of two or more of fluorine, chlorine, bromine, and iodine. For example, X may be a mixture of chlorine and iodine. The combination may include individual components having a concentration of at least about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99 percent. The combination may include individual components having concentrations of up to about 99, 98, 97, 96, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1 percent. For example, the combination may be a mixture of about 1% chlorine and 99% iodine. The combination may include individual components having concentrations within a range defined by any two of the aforementioned values. For example, the combination may be a mixture of about 1% to 5% bromine and about 95% to 99% iodine.

[0145] In the above formula, n1, n2 and n3 may individually be at least about 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.96, 0.97, 0.98, 0.99 or higher. In the above equation, n1, n2, and n3 are individually up to approximately 0.99, 0.98, 0.97, 0.96, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.14, 0.13, 0.12, 0.11, 0.1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.05, 0.01, 0.005, 0.001, 0.0005, It may be 0.0001 or less. In the above formula, n1, n2, and n3 may each have a range defined by any two values. For example, n1 may be about 0.001 to about 0.05, n2 may be about 0.8 to about 0.989, and n3 may be about 0.01 to about 0.15.

[0146] The cation of the chemical formula may be as described above (e.g., methylammonium, formamidinium, cesium, butylammonium). Examples of other cations that may be used include imidazolium, dimethylammonium, guanidinium, ammonium, methylformamidinium, tetramethylammonium, trimethylammonium, rubidium, copper, palladium, platinum, silver, gold, rhodium, ruthenium, sodium, potassium, iron, other inorganic cations, other organic cations, or combinations thereof. The perovskite layer may not contain additional additives. For example, the perovskite layer may not contain thiocyanates. In other examples, the perovskite layer may not contain carbamides. The perovskite layer may be configured to provide high performance and longevity without additional additives. Because there are no additional additives, the perovskite layer can be manufactured more cheaply and easily. Inclusion of cesium cations (or equivalent alternative cations) can improve the thermal stability of the perovskite layer. For example, the presence of cesium can increase the molecular bond strength of the lead halide structure of the perovskite layer. Cesium ions may also have a lower vapor pressure than organic ions, which can contribute to the thermal stability of the perovskite layer. The inclusion of formamidinium may make it more resilient at high temperatures due to its increased molecular weight compared to other organic cations (e.g., methylammonium). Due to the inherent instability of pure formamidinium perovskite containing cesium and / or methylammonium cations, crystal stability can be improved while maintaining thermal stability. Adding too much of a light organic cation (e.g., methylammonium) may reduce thermal stability. Adding butylammonium iodide in a small amount can better passivate defects or imperfections within the crystal due to the larger molecular structure of butylammonium, thereby better filling the gaps in the perovskite crystal structure, which can improve the quality of the perovskite layer and thus achieve a perovskite layer of higher quality or performance.

[0147] The perovskite solar cell may be a perovskite solar cell as described elsewhere in this specification. For example, the perovskite solar cell may be a solar cell formed on top glass of a silicon solar cell. The perovskite layer may maintain at least about 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99 percent of the initial conversion efficiency value after 300 hours of irradiation under 1 solar condition in an atmospheric atmosphere of >25°C and <100°C. The perovskite layer can maintain an initial conversion efficiency value of up to approximately 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, and 10 percent after 300 hours of irradiation under one sun condition in an atmospheric atmosphere of >25°C and <100°C. The perovskite layer can maintain an initial conversion ratio percentage defined by any two of the aforementioned values ​​after 300 hours of irradiation under one sun condition in an atmospheric atmosphere of >25°C and <100°C.

[0148] In another aspect, the present disclosure provides a method. The method may include providing a substrate. A perovskite precursor may be applied to the substrate. The perovskite precursor may be annealed to form a perovskite layer. The perovskite layer is MA n1 FA n2 Cs n3 The composition may include PbX3. MA may be methylammonium. FA may be formamidinium. n1, n2, and n3 may independently be greater than 0 and / or less than 1. n1 + n2 + n3 may be 1. A perovskite solar cell comprising the perovskite layer may maintain a solar conversion efficiency of at least about 80% after 300 hours of irradiation under 1 solar condition in an air atmosphere of >25°C and <100°C. The perovskite layer may undergo an encapsulation lamination process at a temperature of about 120°C or higher. This method may be as described elsewhere in this specification. For example, the method may be process 300 of FIG. 3.

[0149] The temperature of the encapsulation lamination process may be at least about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200℃ or higher. The temperature of the bag lamination process may be up to approximately 200, 190, 180, 170, 160, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15°C. The temperature of the bag lamination process may be within a temperature range defined by any two of the aforementioned values. The bag may be as described elsewhere in this specification (e.g., in relation to the bag material (135) of FIG. 1).

[0150] The perovskite solar cell may be a perovskite solar cell as described elsewhere in this specification. For example, the perovskite solar cell may be a solar cell formed on top glass of a silicon solar cell. The perovskite layer may maintain at least about 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99 percent of the initial conversion efficiency value after 300 hours of irradiation under 1 solar condition in an atmospheric atmosphere of >25°C and <100°C. The perovskite layer can maintain an initial conversion efficiency value of up to approximately 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, and 10 percent after 300 hours of irradiation under one sun condition in an atmospheric atmosphere of >25°C and <100°C. The perovskite layer can maintain an initial conversion ratio percentage defined by any two of the aforementioned values ​​after 300 hours of irradiation under one sun condition in an atmospheric atmosphere of >25°C and <100°C. The perovskite layer can maintain at least about 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99 percent of the initial conversion efficiency value after the encapsulation lamination process. The perovskite layer can maintain an initial conversion efficiency value of up to approximately 99, 98, 97, 96, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 14, 13, 12, 11, and 10 percent or less after the encapsulation lamination process. The perovskite layer can maintain an initial conversion efficiency value defined by any two of the aforementioned arbitrary values ​​after the encapsulation lamination process.

[0151] Perovskite precursors may be applied as described elsewhere in this invention. For example, perovskite precursors may be applied using an ultrasonic spraying process. In this example, the precursors may be applied by different spraying operations (e.g., lead iodide (II) may be applied to the substrate and methylammonium iodide may be applied to the lead iodide). In another example, perovskite precursors may be applied in a single operation. In this example, a solution containing all precursors for the perovskite layer may be applied and annealed to form a perovskite layer. The annealing process may include heating the perovskite layer to a temperature of at least about 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200°C or higher. The annealing process may include heating the perovskite layer to a temperature of up to approximately 200, 190, 180, 170, 160, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15°C. The annealing process may include heating the perovskite layer to a temperature range defined by any two of the aforementioned values.

[0052] The perovskite layer described herein is MA n1 FA n2 Cs n3 It may include a composition of PbX3, where MA is methylammonium and FA is formamidinium. n1 may be a value of about 0.01 to 0.03. n2 may be a value of about 0.82 to 0.94. n3 may be a value of about 0.05 to 0.015. n1 + n2 + n3 may be 1.

[0153] The following examples are intended only to illustrate specific systems and methods described herein and are not intended to be limiting. Example 1 - Preparation of a Perovskite Photovoltaic Cell

[0154] An incoming glass substrate can be coated with indium tin oxide followed by nickel(II) oxide in a pair of physical vapor deposition processes to produce a substrate including a transparent conductive layer and a hole transport layer. Then, the nickel oxide can be laser-scribed to create a template for individual photovoltaics.

[0155] Next, lead iodide (II) in a solution of dimethylformamide and dimethyl sulfoxide can be applied to the hole transport layer via an ultrasonic spraying process. Methylammonium iodide in a solution of dimethylformamide and dimethyl sulfoxide can be applied to the lead iodide (II) via an ultrasonic spraying process. The lead iodide (II) and methylammonium iodide can be annealed to allow the reaction of the two perovskite precursors and the evaporation of the solvent to form a lead iodide methylammonium perovskite layer. A phenyl-C61-butyric acid methyl ester (PCBM) hole transport layer can be applied to the newly formed perovskite layer via an ultrasonic spraying process in a solution of dimethylformamide and dimethyl sulfoxide. Then, the hole transport layer can be laser-etched along the same pattern as the nickel oxide.

[0156] Subsequently, a second transparent conductive layer of indium tin oxide can be applied via physical vapor deposition, and then a silver electrode can be applied by a similar physical vapor deposition process, or in other embodiments, a charge collection tape can be attached directly to the ITO layer. The electrode can be cut via laser scribe to form an electrode assembly, and individual photovoltaic cells can be separated from each other by laser scribe.

[0157] Subsequently, the photovoltaic cell formed as is can be investigated through various measurement techniques, such as scanning electron microscopy (SEM), light absorption / transmission, X-ray diffraction, atomic force microscopy, ellipsometry, electroluminescence spectroscopy, photoluminescence spectroscopy, time-resolved optical spectroscopy, or combinations thereof.

[0158] After applying the second transparent conductive layer, an encapsulant can be applied to the rear surface of the photocell. The encapsulant can be applied before the photocell is separated by laser scribe. A first encapsulant, such as thermoplastic polyolefin, can be applied to the rear surface of the photocell, while a second encapsulant, such as butyl rubber, can be applied to the edges of the photocell. The rear encapsulant can be optically transparent, whereas the side encapsulant can be optically transparent or opaque. For example, a higher-quality encapsulant (e.g., lower moisture and gas permeability) can be placed on the side of the photocell even if it is not optically transparent, because the side of the cell does not absorb light, whereas the encapsulant for the rear of the cell can be transparent to allow light to pass through the bottom bond. Example 2 - Inline generation of a perovskite photovoltaic cell

[0159] Each operation of perovskite photovoltaic production can be integrated into a single device and / or location. For example, the substrate can be placed in a single device that performs all operations of process 300. The perovskite photovoltaic can be integrated with a second photovoltaic (e.g., silicon photovoltaic) in the same device where the perovskite cell was produced. FIG. 10 is an example of an integrated production flow for a perovskite / silicon photovoltaic module. In this example, each operation can be performed on the same production line.

[0160] A glass substrate with a large area (e.g., 1 meter x 2 meters) can be loaded onto a conveyor belt system configured to guide the glass substrate into an enclosure. The enclosure may contain a controlled atmosphere (e.g., low moisture, oxygen content, temperature control, etc.). The enclosure may include a plurality of ultrasonic spray nozzles configured to spray a lead halide solution onto the glass substrate. After applying the lead halide solution, another set of nozzles in the enclosure may apply a methylammonium halide together with a butylammonium halide solution to the lead halide. The conveyor belt may be configured to move the substrate from the lead halide application nozzle to the methylammonium halide / butyl halide solution application nozzle within a set time to allow the formation of lead halide crystals that incorporate the methylammonium halide / butyl halide to form a perovskite layer. After applying the methylammonium halide and butylammonium halide solutions, the substrate may be moved to an annealing oven. In another embodiment, a formulation consisting of lead halide, methylammonium, and formamidinium in a solution of dimethyl sulfoxide and methyl-2-pyrrolidinone (NMP) can be applied as a single formulation via a one-step ultrasonic spray process, followed by an accelerated drying process step by applying a low vapor pressure chemical, such as a diethyl ether chemical, prior to annealing. A substrate can be heated in an annealing oven to form a perovskite layer having predetermined properties (e.g., particle size, thickness, elemental distribution, etc.). The annealing oven can be aligned with a conveyor belt (e.g., the conveyor belt moves through the oven to perform annealing). The annealing oven can be a batch annealing oven (e.g., multiple substrates can be loaded into the oven to be annealed simultaneously). The type of annealing oven can be determined by the cycle time of the oven relative to the annealing period.

[0161] After the formation of the perovskite layer, the substrate can pass through another set of ultrasonic spray nozzles to apply an electron transport layer to the perovskite layer. Subsequently, a second transparent conductive layer can be applied to the electron transport layer via physical vapor deposition, electrodes can be applied via physical vapor deposition, and individual photovoltaic cells can be separated via laser scribe. The entire inline process can take place on a single conveyor belt. Example 3 - Using PDMS as encapsulant

[0162] PDMS can be used as an encapsulant in tandem, 4-terminal, silicon-perovskite solar modules (i.e., the solar module (100) of FIG. 1). During the lamination of perovskite onto silicon solar cells, the PDMS encapsulant was placed between the perovskite solar cells and the silicon solar cells. FIG. 11 shows the light transmittance of various wavelengths through the perovskite solar cells when the PDMS encapsulant is not used. The average transmittance through the top TCO layer is 72.24. The average weighted transmittance is 74.67%. The average weighted transmittance is weighted according to the power delivered by each wavelength of light. The average transmittance through the top glass layer, top TCO layer, and HTL is 72.20%. The average weighted transmittance is 72.68%. The average transmittance through the perovskite solar cells is 29.20%. The average weighted transmittance is 24.34%. When PDMS encapsulant is used, the transmittance for silicon solar cells is improved to 40.44%, and the weighted average is 33.48%.

[0163] Table 1 below shows the improvement in voltage and current characteristics when using PDMS encapsulant. In particular, the short-circuit current density is 13.93 milliamperes per square centimeter ("mA / cm²") when there is an air gap between the perovskite solar cell and the silicon solar cell. 2 It was ) but as the pores were filled with spun-on PDMS, it became 22.72 mA / cm 2It was improved. In Table 1, "EFF" represents efficiency, "FF" represents the fill factor of the current / voltage graph, and "aperture" represents a test of a solar cell illuminated through an aperture where part of the cell blocks the rest of the cell, whereas "cell itself" represents the measurement for the entire cell without an aperture. The battery itself Aperture Spun-on PDMS, Aperture EFF(%) 20.12 5.75 8.54 FF(%) 76 71.9 70.1 Open circuit voltage (Voc) (millivolts) 649.4 573.8 535.7 Short-circuit current density (Jsc) (milliampere / square centimeter) 40.74 13.93 22.72 Maximum voltage (Vmax) (millivolts) 528.4 460.5 421.7 Maximum current density (Jmax) (milliampere / square centimeter) 38.07 12.48 20.25 Short-circuit current (Isc) (ampere) 0.102 0.0163 0.005772 Short-circuit resistance (Rsc) (Ohms) 385.66 327.47 96473 Open circuit resistance (Roc) (Ohms) 0.417 2.8526 4.9478 Area (square centimeters) 2.5 1.17 0.254 Example 4 - Use of PDMS on the upper glass plate

[0164] PDMS can be applied to the top glass plate of a tandem, four-terminal, silicon-perovskite solar module (i.e., the solar module (100) of FIG. 1). Table 2 shows the resulting increase in short-circuit current density when using these various types of PDMS. These improvements are the result of better light trapping and refractive index matching as light travels from air to the perovskite solar cell and through the PDMS to the glass. bare 1:10 Alumina_PDMS Textured 1:50 Alumina_PDMS Textured PDMS EFF 15.39 16.35 16.32 16.83 FF 74.6 75.3 74.9 74.8 Voc 1105.1 1105.5 1117.7 1125 Jsc 18.67 19.63 19.49 20.01 Vmax 900 900 920 920 Jmax 17.1 18.16 17.74 18.3 Isc 0.004741 0.004986 0.004951 0.005083 Rsc 12125 25615 15660 22587 Roc 22.993 20.78 22.156 23.072 area 0.254 Example 5 - Performance of photovoltaic modules with and without an ultra-thin silver layer

[0165] As mentioned in the present disclosure, PVD of the second TCO layer on the ETL can cause defects in both the perovskite layer and the ETL of a tandem, four-terminal, silicon-perovskite photovoltaic module (i.e., the photovoltaic module (100) of FIG. 1). These defects can be minimized by including an ultrathin silver layer deposited at the interface between the ETL and the second TCO layer.

[0166] As illustrated in FIG. 15, the current and voltage (IV) performance of a photovoltaic module having an ultrathin silver layer is superior to that of a photovoltaic module without an ultrathin silver layer. The ultrathin silver layer improves performance due to the additional blocking and shielding effects of silver during the TCO PVD process. Without the silver layer, the photovoltaic module's fill factor (FF) is reduced due to an increase in the number of defect sites at the interface between the second TCO layer and the ETL and / or a large amount of ETL and the perovskite layer during the TCO PVD process.

[0167] Table 3 further shows the improved performance of photovoltaic modules including an ultra-thin silver layer. For example, photovoltaic modules with a silver layer exhibit better efficiency, fill factor, open circuit voltage (Voc), short circuit voltage (Jsc), short circuit current (Isc), short circuit resistance (Rsc), and open circuit resistance (Roc). Example 6 - Performance of a photovoltaic module produced by an inline PVD process

[0168] As described herein, a 4-terminal, silicon-perovskite photovoltaic module (i.e., the photovoltaic module (100) of FIG. 1) can be manufactured using an inline manufacturing process. The inline manufacturing process increases the efficiency of the final photovoltaic module by reducing ion damage and UV exposure to the ETL and perovskite layers during the PVD process.

[0169] Table 4 shows the increase in efficiency of solar modules produced using the inline manufacturing process. Table 4 illustrates specific scenarios (in bold) where the solar modules exhibit high efficiency, fill factor, and open-circuit voltage due to the inline manufacturing process. Table 4 also demonstrates that the inline manufacturing process is sufficiently effective in reducing defects in the ETL and perovskite layers that the addition of an ultrathin silver layer is not strictly necessary. As shown in Table 4, the ultrathin silver layer does not provide the same increase in efficiency as in solar modules not produced using the inline manufacturing process (e.g., comparing the data in Table 4 with the data provided in Table 3). Example 7 - Electrical connection of tandem photovoltaic modules

[0170] Figures 16–19 show examples of various electrical network connections for different types of silicon-perovskite hybrid photovoltaic modules. Detailed insets can explain the electrical connectivity of silicon-perovskite hybrid photovoltaic modules. The leads of the perovskite photovoltaic module can be connected to the leads of the silicon photovoltaic module. For example, the perovskite photovoltaic module may include multiple perovskite solar cell strips connected in series. The silicon solar cells can be connected in a similar manner. This results in two leads coming from the silicon photovoltaic module and two leads coming from the perovskite photovoltaic module. These leads can then be connected together and connected to a junction box to transmit power from the photovoltaic module. This method of connecting silicon photovoltaic modules and perovskite photovoltaic modules to form a hybrid photovoltaic module can be applied to all configurations of silicon and perovskite solar cells. For example, the silicon module may include front-contact silicon solar cells, integrated back-contact silicon solar cells, shingled silicon solar cells, etc. In other examples, the perovskite solar cells may be strip solar cells, tile solar cells, or front-contact solar cells. The perovskite solar cells may include a plurality of cells comprising a plurality of perovskite solar cell strips connected in series. For example, a plurality of cells each comprising a plurality of strips of perovskite solar cells may be connected in parallel in a voltage-matching manner.

[0171] In the example of a hybrid module, a 6 x 10 array of silicon solar cells is electrically connected in series to form a silicon solar cell module having an open-circuit voltage of 0.7 V x 60 = 42 V. A perovskite layer is cut via laser scribe to form 40 strip solar cells. Each strip is approximately 20 mm wide and 300 mm long. The 40 strips are connected in series. These strips can be connected, for example, via a P1 / P2 / P3 layer method. The connected strips can then be connected to each other via electrode / charge collection tapes placed at the ends of the connected strips, as described elsewhere in this specification. Each strip can have an open-circuit voltage of 1.1 V, and the 40 series-connected strips can have a total voltage of 1.1 V x 40 = 44 V. To completely cover the silicon solar panel, five units of the 40 strip solar cells can be tiled onto the same glass plate. Then, the components can be connected in parallel to maintain a voltage-matched state. This effectively enables the creation of a voltage-matched hybrid module. Example 8 - Performance of Mixed Composition Perovskite Solar Cells

[0172] As described elsewhere in this specification, the perovskite layer (e.g., the perovskite layer (120) of FIG. 1) may comprise a mixed composition. The mixed composition can improve the stability of the perovskite layer, thereby improving the overall output of the tandem photovoltaic module. Additionally, the mixed composition may be used to adjust the properties of the perovskite layer for specific applications.

[0173] Figure 21 is a graph illustrating the efficiency of three perovskite solar cells in a reliability test at an extended 85°C and 85% relative humidity (85°C / 85%). This reliability test may be an accelerated aging test capable of demonstrating the long-term stability of the solar cell against moisture or atmospheric infiltration. As shown in Figure 21, the solar cell may show almost no degradation even during long test times. This slow degradation may be due to a combination of the composition of the perovskite layer and the encapsulation quality of the perovskite layer. The module may possess performance that passes standardized test requirements. For example, such modules may pass reliability tests such as IEC 61215 or IEC 61646 standards and may even exceed standard performance (e.g., still passing the standard after 4,000 hours of testing).

[0174] FIGS. 22a and 22b illustrate examples of efficiency degradation of perovskite solar cells under 1-solar irradiation under a dark thermal stress test (Fig. 22a) and a maximum power point thermal stress test (Fig. 22b). Perovskite solar cells containing formamidinium may show little to no degradation in the absence of illumination at 65°C, which demonstrates the enhanced thermal stability imparted by heavier cations compared to the slight thermal degradation of solar cells containing methylammonium. The performance improvement of formamidinium-containing solar cells under illumination at 65°C may be further evident from the fact that the performance loss of formamidinium-containing solar cells is less than one-quarter of the performance loss of methylammonium solar cells.

[0175] The high-temperature aging plots in Figs. 23a–23c are MA 0.2 FA 0.88 Cs 0.1 PbI3's Graphs of open, short, and maximum power point efficiency for perovskite solar cells having different compositions are shown for various temperatures. As shown in Fig. 23b, the mixed composition perovskite exhibits superior performance under the same conditions compared to the corresponding methylammonium-only or formamidinium-only perovskites of Fig. 17b.

[0176] Table 5 is Cs 0.12 FA 0.88 MA 0.02 PbCl 0.01 Br 0.09 I 0.9 This demonstrates the performance of a thermally stable perovskite having the composition. The perovskite solar cell was able to maintain a high photovoltaic conversion efficiency of 18.64% despite relatively high-temperature annealing. This high efficiency demonstrates the high stability achievable in mixed-composition perovskites. Cs 0.12 FA 0.88 MA 0.02 PbCl 0.01 Br 0.09 I 0.9 Types of components opaque translucent Upper ITO NA 40W 23nm, 60W 350nm Post-annealing NA 140℃ Efficiency (%) 19.11 18.64 Fill Factor (%) 77.9 78.6 VOC (mV) 1155.7 1129.6 JSC (mA / cm2) 21.22 21.01 VMAX (mV) 975.1 925.2 JMAX (mA / cm2) 19.59 20.15 I SC (A) 0.0255 0.0273 RSC (Ohm) 1200 8400 ROC (Ohm) 3.83 3.73 A( cm2) 1.2 1.3

[0177] Table 6 illustrates various parameters for perovskite solar cells with different types of edge seals before a high-temperature (e.g., > 120°C) encapsulation lamination process, immediately after lamination, after annealing at 100°C for 10 minutes, and again two days later. The first column provides data for perovskite solar cells without edge seals, the middle column for perovskite solar cells with two sealed edges, and the right column for perovskite solar cells with all four sealed edges. In each case, the perovskite solar cells were able to recover most, if not all, of their original efficiency after annealing. This thermal stability enables the use of higher-quality and higher-temperature encapsulation processes, which can improve the lifespan and efficiency of the solar cells. Example 9 - Scalable manufacturing method for perovskite solar cells

[0178] A spray precursor solution comprising lead halides (II), methylammonium iodide, cesium, formamidinium iodide, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone may be formed as described elsewhere in this invention. For example, the precursor or its salt may be mixed and stirred together and slightly heated to improve homogeneity. The resulting precursor solution may be applied to a substrate via an ultrasonic spraying process and dried at room temperature for 5 to 15 minutes. Then, the substrate with the precursor layer may be immersed in an antisolvent to form a perovskite layer. Examples of immersion include immersion of the substrate in the antisolvent, mechanical spraying of the antisolvent, chemical showering of the antisolvent, or any combination thereof. Slowly adding the perovskite film to the antisolvent may be effective in reducing defects in the film and residues remaining on the film. For example, if the film moves back and forth while being added to the antisolvent bath, defects may occur at the contact line between the film and the antisolvent. To avoid these defects, the substrate can be introduced slowly into the solvent bath. Alternatively, high-quality perovskite films can be produced using controlled pouring rinsing and air knife drying.

[0179] Non-limiting examples of antisolvents include diethyl ether, dibutyl ether, chlorobenzene, chloroform, or any combination thereof. The selection of the antisolvent may depend on the miscibility of the antisolvent and the solvent (e.g., the solvent and the antisolvent may be miscible), the solubility of the perovskite in the antisolvent (e.g., the antisolvent may not effectively dissolve the perovskite), etc. Rapid removal of the solvent through the antisolvent may be important for the overall quality of the film. For example, if the antisolvent does not completely remove the solvent, an impenetrable skin may form on the top of the layer, hindering further solvent removal. In another example, rapid removal of the solvent may result in a high-quality film. The effluent from the immersion can be recovered and recycled (e.g., by removing solid particles) and reused for the production of the next perovskite layer. The perovskite layer may then be annealed as described elsewhere in this specification. For example, the perovskite layer may be annealed at a temperature between 90°C and 110°C for 5-15 minutes, and then annealed at 110°C for 10 minutes. FIG. 24a is an example of a device for producing a perovskite layer including the use of an antisolvent according to one embodiment.

[0180] The method for manufacturing such perovskite films can produce perovskite solar cells with excellent performance and low hysteresis. Table 7 shows examples of the characteristics of perovskite films with a thickness of about 350 nm produced by this method. FIG. 25 illustrates an exemplary histogram of the efficiency of various perovskite layers produced by the method and system described herein according to one embodiment. This figure demonstrates the possibility of producing consistent high-performance perovskite photovoltaic modules for use in the devices described herein. Additional parameter tuning described elsewhere in this specification can further improve the efficiency and consistency of the product perovskite modules.

[0181] A method for preparing a perovskite layer without an antisolvent may involve using a precursor solution comprising lead acetate (II), lead halide (II), methylammonium halide, and dimethylformamide. Such a solution may not require the application of an antisolvent for the formation of the perovskite layer. For example, the solution may be applied to a substrate and dried at room temperature for 5 to 15 minutes to form a perovskite layer. The perovskite layer may be annealed as described elsewhere in this specification. FIG. 24b is an example of a device for producing a perovskite layer without using an antisolvent according to one embodiment.

[0182] This method can be scalable due to a combination of easy atmospheric control (e.g., low humidity ambient conditions), a single-operation perovskite spray formulation, a scalable drying process (e.g., vacuum, air knife, etc.), a scalable annealing process, and the addition of a scalable electron transport layer (e.g., ultrasonic spray formulation and device). Example 10 - Reliability Test and Packaging

[0183] FIG. 26 is a schematic diagram of an exemplary photovoltaic module package according to one embodiment. FIG. 27 is a schematic diagram of an exemplary wiring diagram for a module package according to an embodiment. The exemplary photovoltaic module package may be a hybrid module comprising a perovskite layer (2601) and a silicon layer (2602). The perovskite layer may be formed through methods and systems described elsewhere in this specification. For example, the perovskite layer may be formed on the upper glass plate of a silicon photovoltaic module. The perovskite layer itself may be placed on a hole transport layer on a transparent conductive oxide layer of approximately 7 ohms / square meter as described elsewhere in this specification. An electron transport layer may be added to the perovskite layer, and another transparent conductive oxide layer may be added on the electron transport layer. Then, a metal layer may be added to form electrode contacts configured to remove current from the perovskite layer. The perovskite on the glass can then be overlaid onto a series-connected 2x2 array of 6-inch silicon solar cells. As illustrated, the perovskite solar cells can be connected in parallel with the silicon solar cells. Alternatively, the perovskite and silicon solar cells can be electronically separated (e.g., a four-terminal architecture). The perovskite layer can be arranged with the silicon solar cells in a glass-on-glass configuration. The glass-on-glass configuration can improve light trapping within the photovoltaic module, thereby increasing the overall efficiency of the module. As illustrated in Fig. 27, the perovskite layer can be laser-scribed into multiple strips so that the open-circuit voltage of the perovskite cell ensemble matches the open-circuit voltage of the silicon cells. This voltage matching can reduce waste and improve overall module performance.

[0184] To verify whether the module's performance is maintained over time, the module may be tested. Such tests may include performance tests (e.g., performance measurement, temperature coefficient measurement, normal operating cell temperature measurement, low light irradiation performance, light-induced degradation measurement, light and temperature rise-induced degradation measurement, etc.), environmental durability tests (e.g., temperature cycling, humidity freezing test, moist heat test, potential induced degradation test, etc.), long-term durability tests (e.g., outdoor exposure test, hot spot test, reverse current overload test, UV conditioning, hail durability, etc.), etc., or a combination thereof. computer system

[0185] The present invention provides a computer system programmed to implement the method of the present invention. FIG. 12 illustrates a computer system (1201) programmed to direct the manufacturing and manufacturing processes (e.g., physical vapor deposition, ultrasonic spraying, etc.) described herein, or configured to control power electronic components connected to a photovoltaic module described herein, or configured otherwise.

[0186] The computer system (1201) includes a central processing unit (CPU, also referred to herein as “processor” and “computer processor”) (1205), which may be a single-core or multi-core processor or a plurality of processors for parallel processing. The computer system (1201) also includes memory or memory location (1210) (e.g., random access memory, read-only memory, flash memory), electronic storage device (1215) (e.g., hard disk), communication interface (1220) for communication with one or more other systems (e.g., network adapter), and peripheral devices (1225) such as a cache, other memory, data storage device and / or electronic display adapter. The memory (1210), storage unit (1215), interface (1220), and peripheral devices (1225) communicate with the CPU (1205) via a communication bus (solid line), such as a motherboard. The storage unit (1215) may be a data storage unit (or data storage) for storing data. A computer system (1201) can be operably coupled to a computer network ("network") (1230) with the help of a communication interface (1220). The network (1230) may be the Internet, the Internet and / or extranet, or an intranet and / or extranet communicating with the Internet. In some cases, the network (1230) is a communication and / or data network. The network (1230) may include one or more computer servers capable of enabling distributed computing, such as cloud computing. In some cases, the network (1230) may implement a peer-to-peer network in which a component connected to the computer system (1201) can act as a client or server with the help of the computer system (1201).

[0187] The CPU (1205) may execute a series of machine-readable instructions that may be implemented as a program or software. The instructions may be stored in a memory location such as memory (1210). The instructions may be sent to the CPU (1205), and the CPU (1205) may subsequently be programmed or configured to implement the method of the present invention. Examples of operations performed by the CPU (1205) may include fetching, decoding, executing, and storing.

[0188] The CPU (1205) may be part of a circuit such as an integrated circuit. One or more other components of the system (1201) may be included in the circuit. In some cases, the circuit is an application-specific integrated circuit (ASIC).

[0189] The storage unit (1215) can store files such as drivers, libraries, and stored programs. The storage unit (1215) can store user data, for example, user preferences and user programs. In some cases, the computer system (1201) may include one or more additional data storage elements located outside the computer system (1201), such as being located on a remote server that communicates with the computer system (1201) via an intranet or the internet.

[0190] The computer system (1201) can communicate with one or more remote computer systems through a network (1230). For example, the computer system (1201) can communicate with a user's remote computer system. Examples of remote computer systems may include a personal computer (e.g., a portable PC), a slate or tablet PC (e.g., an Apple® iPad, a Samsung® Galaxy Tab), a telephone, a smartphone (e.g., an Apple® iPhone, an Android-enabled device, a Blackberry®), or a personal digital assistant. The user can access the computer system (1201) through the network (1230).

[0191] The method described herein may be implemented through machine-executable code (e.g., computer processor) stored in an electronic storage location of a computer system (1201), such as memory (1210) or an electronic storage unit (1215). Alternatively, machine-readable code may be provided in the form of software. In use, the code may be executed by the processor (1205). In some cases, the code may be retrieved from the storage unit (1215) and stored in memory (1210) for readiness to be accessed by the processor (1205). In some situations, the electronic storage unit (1215) may be excluded, and the machine-executable instructions are stored in memory (1210).

[0192] The code can be pre-compiled and configured for use with a machine equipped with a processor tuned to execute the code, or it can be compiled at runtime. The code can be provided in a programming language that allows the user to choose to execute the code in a pre-compiled or compiled manner.

[0193] Aspects of the systems and methods provided herein, such as the computer system (1201), may be implemented through programming. Various aspects of the technology may generally be considered as “products” or “manufactured articles” in the form of machine (or processor) executable code and / or related data contained in or implemented on machine-readable media types. Machine executable code may be stored in memory (e.g., read-only memory, random access memory, flash memory) or electronic storage devices such as hard disks. Media of the “storage” type may include some or all of the memory or related modules of a computer, processor, etc., such as various semiconductor memory, tape drives, disk drives, etc., capable of providing non-transient storage for software programming at any time. From time to time, all or part of the software may be transmitted via the Internet or various other communication networks. For example, such communication may load software from one computer or processor to another computer or processor, for example, from a management server or host computer to a computer platform of an application server. Accordingly, other types of media that may contain software elements include optical, electric, and electromagnetic waves, such as those used through physical interfaces between local elements via wired and optical wired networks and various public links. Physical elements that transmit these waves, such as wired or wireless links, optical links, etc., may also be considered as media containing software. As used herein, terms such as computer or machine "readable media" refer to any medium that participates in providing instructions to a processor for execution, unless limited to non-transient types of "storage" media.

[0194] Accordingly, machine-readable media, such as computer-executable code, may take various forms including, but not limited to, tangible storage media, carrier media, or physical transmission media. Non-volatile storage media include, for example, optical or magnetic disks, such as any storage element in any computer, which may be used to implement the database, etc., illustrated in the drawings. Volatile storage media include dynamic memory, such as the main memory of such computer platforms. Tangible transmission media include coaxial cables; copper wires, including wires that constitute buses within a computer system, and optical fibers. Carrier transmission media may take the form of electrical or electromagnetic signals, or acoustic or light waves, such as those generated during radio frequency (RF) and infrared (IR) data communication. Accordingly, common forms of computer-readable media include: floppy disks, flexible disks, hard disks, magnetic tapes, other magnetic media, CD-ROMs, DVDs or DVD-ROMs, other optical media, punch card paper tapes, other physical storage media with a punch pattern, RAM, ROM, PROM and EPROM, FLASH-EPROM, other memory chips or cartridges, carriers that transmit data or instructions, cables or link waves that transmit such carriers, or other media in which a computer can read programming code and / or data. Many of these forms of computer-readable media may be involved in transmitting one or more sequences of one or more instructions to a processor for execution.

[0195] The computer system (1201) may include or communicate with an electronic display (1235) that includes a user interface (UI) (1240) for providing control over manufacturing process parameters, for example. Examples of the UI include, but are not limited to, a graphical user interface (GUI) and a web-based user interface.

[0196] The method and system of the present invention may be implemented through one or more algorithms. The algorithm may be implemented through software when executed by a central processing unit (1205).

[0197] Although preferred embodiments of the present invention have been illustrated and described herein, it will be apparent to those skilled in the art that such embodiments are provided merely as examples. The present invention is not intended to be limited by the specific examples provided in the specification. Although the present invention has been described with reference to the foregoing specification, the description and examples of embodiments in this specification are not to be interpreted in a limiting sense. Numerous modifications, changes, and substitutions will now occur to those skilled in the art without departing from the present invention. Furthermore, it should be understood that all aspects of the present invention are not limited to the specific descriptions, configurations, or relative proportions presented in this specification, which depend on various conditions and variables. It should be understood that various alternatives to the embodiments of the present invention described in this specification may be used to practice the present invention. Accordingly, the present invention is conceived to include such alternatives, modifications, changes, or equivalents. The following claims define the scope of the present invention and are intended to include methods and structures within the scope of these claims and their equivalents.

Claims

Claim 1 A method comprising: (a) a step of forming a perovskite layer on a glass panel, wherein the step of forming the perovskite layer comprises the following steps (i) to (iii); (i) a step of applying a solution to a glass panel to form a solution coating on the glass panel, wherein the solution comprises a perovskite precursor and a solvent; (ii) a step of removing the solvent from the coating to form a perovskite precursor layer on a substrate; and (iii) a step of annealing the perovskite precursor layer at a temperature in the range of 40°C to 120°C to form a perovskite layer, wherein the perovskite layer is MA n1 FA n2 Cs n3 (a) a step having a composition of PbX3, wherein MA is methylammonium, FA is formamidinium, Cs is cesium, Pb is lead, 0.001 ≤ n1 ≤ 0.05, 0 < n2 < 1, 0.001 ≤ n3 ≤ 0.15, n1 + n2 + n3 = 1, and X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; (c) a step of fabricating one or more perovskite solar cells from the perovskite layer, wherein one or more perovskite solar cells generate a first output voltage; and (d) a step of stacking one or more perovskite solar cells onto a silicon solar cell module so that the glass panel forms an upper glass panel of the silicon solar cell module, wherein the silicon solar cell module has a second output voltage and the first output voltage matches the second output voltage; and (e) electrically connecting the silicon photovoltaic module to one or more perovskite solar cells. Claim 2 A method according to claim 1, wherein the fabrication step (c) comprises the step of using a laser scribe to define one or more perovskite solar cells. Claim 3 A method according to claim 1, wherein the one or more perovskite solar cells are a plurality of perovskite solar cells. Claim 4 In paragraph 3, the method of connecting the plurality of perovskite solar cells in series. Claim 5 A method according to claim 1, further comprising the step of applying a plurality of contacts to one or more perovskite solar cells to electrically couple to the one or more perovskite solar cells. Claim 6 A method according to claim 1, further comprising the step of applying an encapsulation material to one or more perovskite solar cells. Claim 7 In claim 6, the method wherein the above-mentioned encapsulant is a thermoplastic polyolefin. Claim 8 In claim 7, the method wherein the bag material is ethyl-vinyl acetate. Claim 9 A method according to claim 1, further comprising the step of applying an edge sealant to one or more perovskite solar cells. Claim 10 A tandem photovoltaic module comprising: (i) a plurality of silicon solar cells connected in series and (ii) a silicon solar panel including an upper glass plate wherein the plurality of silicon solar cells are connected in series and combined to have a first open-circuit voltage; and a perovskite solar panel disposed below the upper glass plate of the silicon solar panel, wherein the perovskite solar panel comprises a plurality of segments, and each of the plurality of segments comprises a plurality of laser-scribe strips of perovskite, wherein the plurality of laser-scribe strips of perovskite within the segment are connected in series to generate a second open-circuit voltage equal to the first open-circuit voltage, and wherein the perovskite is MA n1 FA n2 Cs n3 A tandem photovoltaic module comprising: a perovskite photovoltaic panel having a composition of PbX3, wherein MA is methylammonium, FA is formamidinium, Cs is cesium, Pb is lead, 0.001 ≤ n1 ≤ 0.05, 0 < n2 < 1, 0.001 ≤ n3 ≤ 0.15, n1 + n2 + n3 = 1, and X is selected from the group consisting of fluorine, chlorine, bromine, and iodine, wherein the perovskite photovoltaic panel maintains a solar conversion efficiency of 80% or more after 300 hours of irradiation under 1 solar condition in an air atmosphere of > 25℃ and < 100℃; and an interconnect connecting the plurality of silicon solar cells and the plurality of segments of the perovskite photovoltaic panel in parallel. Claim 11 In claim 10, the plurality of segments comprises a tandem photovoltaic module including 10 to 200 segments. Claim 12 In paragraph 10, the silicon solar panel is a tandem solar module that is a top contact solar panel, an integrated back contact solar panel, or a shingled solar panel. Claim 13 In claim 10, the silicon solar panel and the perovskite solar panel are connected to the same junction box in a tandem solar module. Claim 14 In claim 10, the silicon solar panel and the perovskite solar panel are tandem solar modules having similar areas. Claim 15 In claim 10, the plurality of laser-scribe strips of perovskite are tandem photovoltaic modules connected through a P1 / P2 / P3 system. Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete Claim 31 delete Claim 32 delete Claim 33 delete Claim 34 delete Claim 35 delete Claim 36 delete Claim 37 delete Claim 38 delete Claim 39 delete Claim 40 delete Claim 41 delete Claim 42 delete Claim 43 delete Claim 44 delete Claim 45 delete Claim 46 delete Claim 47 delete Claim 48 delete Claim 49 delete Claim 50 delete Claim 51 delete Claim 52 delete Claim 53 delete Claim 54 delete Claim 55 delete Claim 56 A method according to claim 1, wherein the glass panel comprises a hole transport layer and the solution is applied to the surface of the glass panel. Claim 57 The method of claim 1, wherein the perovskite precursor comprises an organic halide and a metal halide selected from the group consisting of formamidinium chloride, formamidinium bromide, formamidinium iodide, methylammonium chloride, methylammonium bromide, methylammonium iodide, and butylammonium halide. Claim 58 A method according to claim 1, wherein the solvent is a mixture of at least two solvents. Claim 59 A method according to claim 58, wherein the at least two solvents have different evaporation rates when removing the solvent from the coating. Claim 60 In paragraph 58, the method wherein the first of at least two solvents is dimethyl sulfoxide. Claim 61 A method according to claim 1, wherein the step of fabricating one or more perovskite solar cells from a perovskite layer includes the step of applying an electron transport layer to the perovskite layer. Claim 62 A method according to claim 61, wherein the step of fabricating one or more perovskite solar cells from a perovskite layer further comprises the step of forming a transparent conductive layer on an electron transport layer. Claim 63 A method according to claim 61, wherein the step of forming a transparent conductive layer comprises the step of forming a buffer layer of a transparent conductive oxide on an electron transport layer with a first power using a physical vapor deposition process, and then forming a bulk layer of a transparent conductive oxide on the buffer layer with a second power greater than the first power using a physical vapor deposition process. Claim 64 A method according to claim 61, wherein the step of fabricating one or more perovskite solar cells further comprises the step of treating the perovskite layer, the electron transport layer, and the transparent conductive layer by an encapsulation lamination process at a temperature of at least 70°C and up to 130°C. Claim 65 A method according to claim 1, wherein a perovskite layer in one or more solar cells maintains at least 80% of the initial solar conversion efficiency after 300 hours of irradiation under 1 solar conditions of > 25°C and < 100°C.

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