CN116547104A - Method and apparatus for integrated stacked solar module fabrication - Google Patents

Method and apparatus for integrated stacked solar module fabrication Download PDF

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Publication number
CN116547104A
CN116547104A CN202180064458.1A CN202180064458A CN116547104A CN 116547104 A CN116547104 A CN 116547104A CN 202180064458 A CN202180064458 A CN 202180064458A CN 116547104 A CN116547104 A CN 116547104A
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perovskite
layer
solar cell
silicon
silicon solar
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Inventor
朱恩·本杰明·恒
李正哲
黄景顺
约翰·伊纳利
利亚姆·索恩根
布莱恩·D·亨特
埃里克·W·汪
周晨宇
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Selous Co
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Selous Co
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Priority claimed from PCT/US2021/051465 external-priority patent/WO2022066707A1/en
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Abstract

The present disclosure may provide methods and apparatus for a stacked perovskite solar module. The perovskite solar module may include a plurality of perovskite solar cells configured to match the voltage output of another solar module. The present disclosure may provide a mixed composition perovskite layer. Solar cells fabricated using the mixed composition perovskite layer may exhibit improved performance and stability.

Description

Method and apparatus for integrated stacked solar module fabrication
Cross reference
U.S. provisional patent application number 63/081,747 filed on the year 2020 month 22, U.S. provisional patent application number 63/081,750 filed on the year 2020 month 22, U.S. provisional patent application number 63/081,753 filed on the year 2020 month 22, U.S. provisional patent application number 63/081,758 filed on the year 2020 month 22, U.S. provisional patent application number 63/081,756 filed on the year 2020 month 22, U.S. provisional patent application number 63/081,755 filed on the year 2020 month 22, U.S. provisional patent application number 63/081,752 filed on the year 2020 month 12, U.S. provisional patent application number 63/090,636 filed on the year 2020 month 10 month 12, U.S. provisional patent application number 63/090,643 filed on the year 2020 month 12 month 16, U.S. provisional patent application number 63/126,481 filed on the year 2020 month 12, U.S. provisional patent application number 63/2023,2023, and U.S. provisional patent application number 1,57 to the year 1,2012 are filed on the whole, and U.S. provisional patent application number 63/passing through year 1,2012, and U.S. provisional patent application number 3,57 to be filed on the year 1,57.
Technical field and background art
Solar cells are electrical devices that convert light into electricity. Silicon solar cells may be capable of converting light having wavelengths greater than about 300 nanometers ("nm") and less than about 1100nm into electricity. However, as the wavelength of light decreases from 1100nm, the conversion efficiency of silicon solar cells may become worse. Furthermore, silicon solar cells may not be able to convert light having a wavelength greater than about 1100nm into electricity because such wavelength of light lacks the energy required to overcome the bandgap of silicon.
A stacked solar cell may have two individual solar cells stacked together. The bottom cell may be a silicon solar cell and the top cell may be made of different materials. The top cell may have a higher bandgap than the silicon solar cell. Thus, the top cell is able to efficiently convert shorter wavelength light into electricity. The top cell may be transparent to longer wavelength light, which may allow the underlying silicon solar cell to absorb this longer wavelength light and convert it to electricity.
Optical losses at the interface between the top and bottom cells and recombination losses in any layer of the top or bottom cell may result in reduced cell efficiency. Furthermore, stacked solar cells can be difficult to manufacture.
Disclosure of Invention
The present disclosure describes a stacked silicon-perovskite solar module and a method of manufacturing the same. The stacked silicon-perovskite solar modules 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 electron volts ("eV"), and the silicon solar cell may have a bandgap of about 1.1 eV. Thus, the perovskite solar cell may be capable of efficiently converting light of a shorter wavelength into electricity. The perovskite solar cell may be transparent to longer wavelength light, which may allow the underlying silicon solar cell to absorb such longer wavelength light and convert it to electricity. The perovskite solar cell and silicon solar cell together may be able to efficiently convert a broader spectrum of light into electricity (i.e., thermalization losses in a stacked cell may be less than in a single cell solar module, resulting in higher full spectral efficiency) compared to a single solar cell. The addition of perovskite solar cells may improve the resulting solar module by reducing cost, improving the performance of the module per unit weight, improving the overall performance of the module, and the like.
The silicon solar cell may be a monocrystalline or polycrystalline silicon solar cell. The silicon solar cell may be a component of a conventional solar panel. The solar panel may have a back sheet on which the silicon solar cells are disposed. An encapsulant may cover the top of the silicon solar cell to prevent its exposure to dust and moisture. The solar panel may also have a top glass plate to provide additional protection for the silicon solar cell.
The perovskite solar cell may be deposited on a bottom surface of the top glass sheet. This may be different from the construction of conventional stacked solar modules in which only perovskite cells are arranged on top of a silicon wafer. Depositing the perovskite solar cells on the bottom surface of the top glass sheet may allow manufacturers to incorporate perovskite solar cells into their conventional silicon solar panels without the need to update the equipment or change the process. Instead, these manufacturers may replace only conventional glass sheets with perovskite glass sheets. The present disclosure may refer to the perovskite glass sheet as "active glass".
The perovskite solar cell may have a first transparent conductive oxide ("TCO") layer deposited on the top glass sheet, 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 may serve as terminals of the perovskite solar cell. The ETL and HTL may promote electron and hole transport, respectively, while inhibiting hole and electron transport, respectively. The perovskite layer may absorb light to generate charge carriers, which results in voltage and current flow across the terminals of the perovskite solar cell.
The perovskite solar cell and the silicon solar cell may be electrically insulated from each other, and each cell may have its own terminal. That is, the stacked solar module may be a 4-terminal module. The perovskite solar cell and the silicon solar cell may be connected in series or in parallel by connecting the terminals in a suitable manner. In the case of a series connection, the perovskite solar cell and the silicon solar cell may be current matched. In case of parallel connection, the perovskite solar cell and the silicon solar cell may be voltage matched.
The present disclosure also describes methods of making the above-described reactive glasses. The reactive glass may comprise a perovskite layer formed by separately applying perovskite precursors and subsequently annealing the precursors. A metallic lead layer may be deposited followed by an inorganic halide layer (e.g., methyl ammonium iodide/formamidine iodide) followed by a halide ion (e.g., iodine). By applying the various precursors in this manner, the same deposition apparatus can be used for multiple layers, reducing complexity and cost, and enabling the use of high throughput manufacturing processes. In addition, the various ratios of the precursors can be tightly controlled, resulting in higher quality films. In addition, a variety of different precursors may be deposited for each layer to improve film quality. For example, lead acetate may be applied over the lead layer to improve the incorporation of organic halides and halide ions into the lead layer. Also, different halide ions may be introduced to improve grain growth and other film properties. The perovskite precursor may be applied by a variety of different techniques including ultrasonic spraying, knife coating, slot die coating and physical vapor deposition. When combined with multiple "spray head" nozzles, ultrasonic spraying can provide uniform and controlled precursor application, which in turn can produce a high quality film that is substantially defect free.
The present disclosure also provides methods of depositing the first and second TCO layers on the perovskite solar cell. The TCO layer may be deposited on the perovskite solar cell by Physical Vapor Deposition (PVD). PVD of the TCO layer can be performed during inline fabrication. The inline fabrication process may include a plurality of process compartments in which deposition of a selected target material on the perovskite solar cell occurs. The plurality of process compartments may comprise a single conveyor belt transporting the perovskite solar cell in the plurality of process compartments. The inline fabrication process may limit the exposure of the perovskite solar cell to the deposition process and direct exposure of Ultraviolet (UV) radiation and ultimately reduce the number of defects formed in the ETL and perovskite layers due to the TCO deposition process.
The present disclosure also provides a method of connecting layers of a stacked solar module. The silicon and perovskite layers of the laminate module may be connected in different ways depending on the type of silicon solar cell used. Different connection methods can provide optimal performance for a variety of different types of silicon solar cells. The present disclosure also provides a method of making a stacked solar module in which the voltage outputs of the top perovskite and bottom silicon modules are matched. The method may include laser scribing a perovskite layer to form the perovskite solar cell. The laser scribing may be different for different bottom solar modules, as voltage output differences for various different bottom modules may be taken into account in the production of the perovskite solar cell. Such a control level may improve efficiency by more closely matching the voltage between the modules to reduce wasted voltage. Furthermore, a wider range of bottom modules may be used due to the flexibility provided by customizing the perovskite solar cell size.
In one aspect, the present disclosure provides an apparatus comprising: a silicon solar cell having a first bandgap; a glass sheet covering the silicon solar cell, wherein the glass sheet comprises a top surface and a bottom surface; and a perovskite solar cell having a second bandgap, wherein the perovskite solar cell is deposited on the bottom surface of the glass sheet. In certain embodiments, the silicon solar cell is electrically insulated from the perovskite solar cell. In certain embodiments, the silicon solar cell comprises two terminals and the perovskite solar cell comprises two terminals. In certain embodiments, the perovskite solar cell comprises a photoactive perovskite layer, wherein the photoactive perovskite layer comprises CH 3 NH 3 PbX 3 Or H 2 NCHNH 2 PbX 3 . In certain embodiments, X comprises iodine, bromine, chloride ions, or a combination thereof. In certain embodiments, the perovskite solar cell comprises a first Transparent Conductive Oxide (TCO) layer and a second TCO layer. In certain embodiments, the first TCO layer and the second TCO layer are terminals of the perovskite solar cell. In certain embodiments, the first and second TCO layers comprise indium oxide. In certain embodiments, the perovskite solar cell comprises an Electron Transport Layer (ETL) comprising methyl phenyl-C61-butyrate. In certain embodiments, the perovskite solar cell comprises a Hole Transport Layer (HTL) comprising nickel oxide. In certain embodiments, the device further comprises a plurality of silicon solar cells including the silicon solar cell and a plurality of perovskite solar cells including the perovskite solar cell, wherein the plurality of perovskite solar cells are laser scribed in the top glass sheet to match the plurality of perovskite solar cells to the plurality of silicon solar cell voltages Or current matching. In certain embodiments, the top glass sheet has a surface area that substantially corresponds to the surface area of a 60 or 72 cell solar panel. In certain embodiments, the top surface of the top glass sheet comprises an anti-reflective coating. In certain embodiments, the top surface of the top glass sheet comprises Polydimethylsiloxane (PDMS). In certain embodiments, the PDMS comprises 1:10 alumina PDMS, textured 1:50 alumina PDMS, or textured PDMS. In certain embodiments, the bottom surface of the top glass sheet has a textured surface. In certain embodiments, the device further comprises an encapsulant disposed between the silicon solar cell and the perovskite solar cell. In certain embodiments, the encapsulant is selected from the group consisting of ethylene vinyl acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, and paraffin. In certain embodiments, the silicon solar cell and the perovskite solar cell are electrically connected in parallel. In certain embodiments, the silicon solar cell and the perovskite solar cell are electrically connected in series. In certain embodiments, the second bandgap is between about 1.5 and 1.9 electron volts (eV). In certain embodiments, the device has a power conversion efficiency of at least about 30%. In certain embodiments, the silicon solar cell is selected from the group consisting of single crystal solar cells, polycrystalline solar cells, passivated emitter back contact (PERC) solar cells, interdigitated back contact cells (IBC), and heterojunction with intrinsic thin layer (HIT) solar cells.
In another aspect, the present disclosure provides an apparatus comprising: a silicon solar cell having a first bandgap; a perovskite solar cell having a second bandgap, wherein the perovskite solar cell is configured adjacent to the silicon cell, and wherein the device has a power conversion efficiency of at least about 26%. In certain embodiments, the silicon solar cell is electrically insulated from the perovskite solar cell. In certain embodiments, the silicon solar cell comprises two terminals and the perovskite solar cell comprises two terminals. In certain embodiments, the perovskite solar cell comprises a photoactive perovskite layerWherein the photoactive perovskite layer comprises CH 3 NH 3 PbX 3 Or H 2 NCHNH 2 PbX 3 . In certain embodiments, X comprises iodine, bromine, chloride ions, or a combination thereof. In certain embodiments, the perovskite solar cell comprises a first Transparent Conductive Oxide (TCO) layer and a second TCO layer. In certain embodiments, the first TCO layer and the second TCO layer are terminals of the perovskite solar cell. In certain embodiments, the first and second TCO layers comprise indium oxide, indium tin oxide, or aluminum zinc oxide. In certain embodiments, the perovskite solar cell comprises an Electron Transport Layer (ETL) comprising phenyl-C61-butyrate or C60. In certain embodiments, the perovskite solar cell comprises a Hole Transport Layer (HTL) comprising nickel oxide. In certain embodiments, the device further comprises an encapsulant disposed between the silicon solar cell and the perovskite solar cell. In certain embodiments, the encapsulant is selected from the group consisting of ethylene vinyl acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, and paraffin. In certain embodiments, the silicon solar cell and the perovskite solar cell are electrically connected in parallel. In certain embodiments, the silicon solar cell and perovskite solar cell are electrically connected in series. In certain embodiments, the second bandgap is between about 1.5 and 1.9 electron volts (eV). In certain embodiments, the silicon solar cell is selected from the group consisting of single crystal solar cells, polycrystalline solar cells, passivated emitter back contact (PERC) solar cells, interdigitated back contact cells (IBC), and heterojunction with intrinsic thin layer (HIT) solar cells.
In another aspect, the present disclosure provides a method for forming a transparent conductive layer of a solar cell, the method comprising: (a) Using up to about 0.6 watts per square centimeter (W/em) 2 ) Depositing a buffer layer of the transparent conductive layer on the solar cell; and (b) using up to about 1W/em 2 Depositing a bulk layer of the transparent conductive layer on the buffer layer. In certain embodiments, (a) and (b) comprise physical vapor depositionAnd (5) processing. In certain embodiments, the buffer layer is at least 5 nanometers thick. In certain embodiments, the method further comprises depositing a silver layer on the solar cell prior to (a). In certain embodiments, the silver layer is up to about 10 angstroms thick. In certain embodiments, the method further comprises annealing the transparent conductive layer.
In another aspect, the present disclosure provides a method for forming a perovskite layer of a solar cell, the method comprising: (a) Depositing a metallic lead (Pb) layer on top glass of the solar cell by physical vapor deposition; (b) Applying a layer of Methyl Ammonium Iodide (MAI) or formamidine iodide (FAI) on the metallic Pb layer by ultrasonic spraying; and (c) exposing the MAI or FAI layer to iodine gas by translating a dispensing unit through the MAI or FAI layer, wherein the dispensing unit comprises a plurality of nozzles configured to provide iodine gas. In certain embodiments, the method further comprises applying a Pb salt to the metallic lead layer prior to (b). In certain embodiments, the lead salt comprises one or more salts selected from lead (II) acetate, lead (II) chloride, lead (II) bromide, and lead (II) iodide. In certain embodiments, the MAI or FAI layer comprises a methyl ammonium chloride (MACl) additive. In certain embodiments, the method further comprises applying a phenylethyl ammonium iodide (pei) solution to the MAI or FAI layer. In certain embodiments, (a) - (c) are performed in a compartment that is not reactive to iodine gas. In certain embodiments, the compartments are made of glass. In certain embodiments, the compartments are made of titanium. In certain embodiments, the method further comprises (d) performing one or more annealing operations to form the perovskite layer from the metal Pb layer, MAI or FAI layer, and iodine gas. In certain embodiments, the plurality of nozzles is one or more shower-head nozzles.
In another aspect, the present disclosure provides a method for forming a perovskite layer of a solar cell, the method comprising: (a) Applying a lead halide layer comprising lead iodide, lead bromide, and lead chloride on the solar cell using an ultrasonic dispensing unit comprising a plurality of nozzles; and (b) applying a layer of methyl ammonium halide on the lead halide layer using the ultrasonic dispensing unit. In certain embodiments, the lead halide layer comprises more lead chloride than lead bromide by weight.
In another aspect, the present disclosure provides a method comprising: (a) Providing a silicon solar module having a first voltage output, wherein the silicon solar module comprises a top glass panel; (b) forming a perovskite layer on the top glass panel; (c) Fabricating one or more perovskite solar cells from the perovskite layer, wherein the one or more perovskite solar cells produce a voltage that substantially matches a voltage output of the silicon solar module; and (d) electrically connecting the silicon solar module with the one or more perovskite solar cells.
In certain embodiments, the fabricating includes using laser scribing to define the one or more perovskite solar cells. In certain embodiments, the one or more perovskite solar cells are a plurality of perovskite solar cells. In certain embodiments, the plurality of perovskite solar cells are connected in series. In certain embodiments, the method further comprises applying a plurality of contacts to the one or more perovskite solar cells to electrically couple the one or more perovskite solar cells. In certain embodiments, the method further comprises applying an encapsulant to the one or more perovskite solar cells. In certain embodiments, the encapsulant is a thermoplastic polyolefin. In certain embodiments, the thermoplastic polyolefin is ethylene vinyl acetate. In certain embodiments, the method further comprises applying an edge seal to the one or more perovskite solar cells.
In another aspect, the present disclosure provides a stacked solar module. The laminated solar module may include: a silicon solar panel comprising (i) a plurality of silicon solar cells connected in series and (ii) a top glass plate, wherein the plurality of silicon solar cells are connected in series and together have a first open circuit voltage; a perovskite solar panel configured on a bottom surface of a top glass sheet of the silicon solar panel, wherein the perovskite solar panel comprises a plurality of sections, wherein each section of the plurality of sections comprises a plurality of laser-scribed perovskite strips, wherein the plurality of laser-scribed perovskite strips within the section are connected in series to produce a second open circuit voltage that is substantially the same as the first open circuit voltage; and an interconnect connecting the plurality of silicon solar cells in parallel with the plurality of sections of the perovskite solar panel.
In certain embodiments, the plurality of segments comprises from about 10 to about 200 segments. In certain embodiments, the silicon solar panel is a top contact solar panel, an integrated back contact solar panel, or a roof solar panel. In certain embodiments, the silicon solar panel and the perovskite solar panel are connected to the same junction box. In certain embodiments, the silicon solar panel and the perovskite solar panel have substantially similar areas. In certain embodiments, the plurality of laser-scribed perovskite strips are connected by a P1/P2/P3 scheme.
In another aspect, the present disclosure provides a perovskite layer comprising: MA (MA) n1 FA n2 Cs n3 PbX 3 Wherein MA is methyl ammonium, FA is formamidine, n1, n2, and n3 are independently greater than 0 and less than 1, and n1+n2+n3=1, wherein a perovskite solar cell comprising the perovskite layer maintains at least about 80% solar conversion efficiency after 300 hours of irradiation in an air atmosphere at > 25 ℃ and < 100 ℃ under 1sun conditions.
In certain embodiments, X is selected from fluorine, chlorine, bromine, and iodine. In certain embodiments, X is a combination of two or more of fluorine, chlorine, bromine, and iodine. In certain embodiments, n1 is from about 0.001 to about 0.05. In certain embodiments, n3 is from about 0.001 to about 0.15. In certain embodiments, the solar conversion efficiency is at least about 90% of the initial conversion efficiency value after 300 hours of irradiation under 1sun condition. In certain embodiments, the solar conversion efficiency is at least about 95% of the initial conversion efficiency value after 300 hours of irradiation under 1sun condition. In certain embodiments, the perovskite layer does not comprise additional additives.
In another aspect, the present disclosure provides a method comprising: (a) providing a substrate; (b) applying a perovskite precursor to the substrate; (c) Annealing the perovskite precursor to form a perovskite layer; wherein the perovskite layer has MA n1 FA n2 Cs n3 PbX 3 Wherein n1, n2, and n3 are independently greater than 0 and less than 1, and n1+n2+n3=1, wherein a perovskite solar cell comprising the perovskite layer maintains at least about 80% solar conversion efficiency after 300 hours of irradiation at 1sun condition at > 25 ℃ and < 100 ℃; and (d) subjecting the perovskite layer to an encapsulation lamination process at a temperature of at least about 120 ℃.
In certain embodiments, the perovskite solar cell retains at least about 80% of the initial conversion efficiency value after the encapsulation lamination process. In certain embodiments, the perovskite solar cell retains at least about 97% of the initial conversion efficiency value after the encapsulation lamination process. In certain embodiments, the application of the perovskite precursor is performed by an ultrasonic spray process. In certain embodiments, the annealing process includes heating the perovskite layer to a temperature of at least about 40-120 ℃.
In another aspect, the present disclosure provides a perovskite layer comprising: MA (MA) n1 FA n2 Cs n3 PbX 3 Wherein MA is methyl ammonium, FA is formamidine, 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.
In certain embodiments, X is selected from fluorine, chlorine, bromine, and iodine. In certain embodiments, X is a combination of two or more of fluorine, chlorine, bromine, and iodine. In certain embodiments, the perovskite solar cell does not comprise additional additives.
Other aspects of the disclosure provide methods of making and producing the devices and components described above and elsewhere in the disclosure.
Other aspects and advantages of the present disclosure will become apparent to those skilled in the art from the following detailed description, which, by way of example, illustrates and describes only exemplary embodiments of the disclosure. As will be realized, the present disclosure is capable of other and different embodiments and its several details are capable of modification in various obvious respects, all without departing from the present disclosure. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
Incorporated by reference
All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. If a publication or patent application, which is incorporated by reference, contradicts the disclosure contained in this specification, this specification is intended to supersede and/or take precedence over any such contradictory material.
Drawings
The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings (also referred to herein as "figures") of which:
FIG. 1 schematically illustrates a stacked, 4-terminal, silicon-perovskite solar cell according to one embodiment;
FIG. 2 schematically illustrates the formation of a perovskite layer of a solar cell according to one embodiment;
fig. 3 is a flow chart of a manufacturing process for forming a perovskite photovoltaic cell according to one embodiment of the disclosure;
FIG. 4 is a flowchart of operation 310 of FIG. 3, according to one embodiment;
FIG. 5 is a flowchart of operation 340 of FIG. 3, according to one embodiment;
FIG. 6 is a flowchart of operations 350 of FIG. 3, according to one embodiment;
FIG. 7 is a flowchart of operation 360 of FIG. 3, according to one embodiment;
FIG. 8 schematically illustrates perovskite precursor deposition compartments according to one embodiment;
FIG. 9 schematically illustrates a showerhead design of a spray nozzle according to one embodiment;
FIG. 10 schematically illustrates an integrated production flow of perovskite photovoltaic cells according to one embodiment;
FIG. 11 illustrates the transmission of light of various different wavelengths through a perovskite solar cell according to one embodiment;
FIG. 12 illustrates a computer system programmed or otherwise configured to perform the methods provided herein;
FIG. 13 is a flow chart of a manufacturing method for forming a perovskite layer according to one embodiment;
FIG. 14 illustrates a horizontal inline manufacturing system in accordance with one embodiment;
FIG. 15 is a graph showing current-voltage performance of solar modules fabricated with and without ultra-thin silver layers according to one embodiment;
FIGS. 16-19 illustrate examples of different electrical network connections for different types of silicon-perovskite hybrid solar modules according to certain embodiments;
FIG. 20 is a flow chart of a process of manufacturing a stacked solar module according to some embodiments;
FIG. 21 is a graph showing the efficiency of three perovskite solar cells during reliability testing at 85 ℃ and 85% relative humidity according to one embodiment;
FIGS. 22A-22B illustrate examples of efficiency degradation of perovskite solar cells under dark thermal stress testing and under 1-sun illumination at maximum power point thermal stress testing, according to one embodiment;
23A-23C illustrate open, short, and maximum power point efficiency plots of a perovskite solar cell at various different temperatures, according to one embodiment;
FIGS. 24A-24B illustrate examples of apparatus for generating a perovskite layer including use of an anti-solvent and no use of an anti-solvent, respectively, according to certain embodiments;
FIG. 25 illustrates an exemplary histogram of the efficiency of various perovskite layers produced by the methods and systems described herein, according to one embodiment;
FIG. 26 is a schematic diagram of an exemplary solar module package according to one embodiment; and is also provided with
Fig. 27 is a schematic diagram of an exemplary wiring diagram of a module package according to one embodiment.
Detailed Description
While various embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions will now occur to 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 employed.
The term "at least," "greater than," or "greater than or equal to" when used in reference to a first value appearing in a series of two or more values applies to each value in the series. For example, 1, 2, or 3 or more is equivalent to 1 or more, 2 or 3 or more.
The term "no more," "less than," or "less than or equal to" when used in reference to a first value appearing in a series of two or more values applies to each value in the series. For example, less than or equal to 3, 2, or 1 is equivalent to less than or equal to 3, less than or equal to 2, or less than or equal to 1.
As used herein, the term "solar cell" generally refers to a device that utilizes the photovoltaic effect to generate electricity from light.
As used herein, the term "stack" refers to a solar module having two solar cells stacked together.
As used herein, the term "4-terminal" refers to a stacked solar module in which the top and bottom solar cells each have two accessible terminals.
When in the bookAs used herein, the term "perovskite" generally refers to a material having a crystal structure similar to perovskite oxide, and which is suitable for use in perovskite solar cells. The general chemical form of perovskite materials is ABX 3 . Examples of perovskite materials include lead methyl ammonium trihalide (i.e., CH 3 NH 3 PbX 3 Wherein X is a halide such as iodine, bromine or chlorine and lead trihaloformamidine (i.e., H) 2 NCHNH 2 PbX 3 Wherein X is a halide such as iodine, bromine or chloride).
As used herein, the term "single crystal silicon" generally refers to silicon having a uniform crystal structure throughout the material. The orientation, lattice parameter, and electronic properties of single crystal silicon may be constant throughout the material. Monocrystalline silicon may be doped with, for example, phosphorus or boron to produce n-type or p-type silicon, respectively.
As used herein, the term "polysilicon" generally refers to silicon having an irregular grain structure.
As used herein, the term "passivated emitter back contact (PERC) solar cell" generally refers to a solar cell having an additional dielectric layer on the back side of the solar cell. The dielectric layer may be used to reflect unabsorbed light back to the solar cell for a second absorption attempt and may additionally passivate the back surface of the solar cell, improving the efficiency of the solar cell.
As used herein, the term "heterojunction with intrinsic thin layer (HIT) solar cell" generally refers to a solar cell composed of a single-crystal silicon wafer surrounded by an ultra-thin amorphous silicon layer. One amorphous silicon layer may be n-doped and the other p-doped.
As used herein, the term "interdigitated back contact cell (IBC)" generally refers to a solar cell that includes two or more electrical contacts configured on the back side of the solar cell (e.g., on the side opposite the incident light). The two or more electrical contacts may be configured adjacent to alternating n-and p-doped regions of the solar cell. IBCs may include high quality absorbing materials configured to allow long distance migration of carriers.
As used herein, the term "bandgap" generally refers to the energy difference between the top of the valence band and the bottom of the conduction band in a material.
As used herein, the term "electron transport layer" ("ETL") generally refers to a layer of material that promotes electron transport and inhibits hole transport in a solar cell. Electrons may be majority carriers in the ETL and holes may be minority carriers. The ETL may be composed of one or more n-type layers. The one or more n-type layers may include an n-type exciton blocking layer. The n-type exciton blocking layer may have a wider band gap than the photoactive layer (e.g., perovskite layer) of the solar cell, but the conduction band closely matches the conduction band of the photoactive layer. This may allow electrons to be easily transported from the photoactive layer to the ETL.
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 undoped. The metal oxide may be an oxide of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, cadmium or a mixture of two or more of these metals. The metal sulfide may be a sulfide of cadmium, tin, copper, zinc, or a mixture of two or more of these metals. The metal selenide may be a selenide of cadmium, zinc, indium, gallium, or a selenide of a mixture of two or more of the metals. The metal telluride may be a cadmium, zinc, cadmium or tin telluride, or a telluride of a mixture of two or more of said metals. Alternatively, other n-type materials may be used, including organic and polymeric electron transporting materials and electrolytes. Suitable examples include, but are not limited to, fullerenes or fullerene derivatives (e.g., methyl phenyl-C61-butyrate, C60, etc.) or organic electron transporting materials comprising perylenes or derivatives thereof.
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 may be majority carriers in the HTL and electrons may be minority carriers. The HTL may be composed of one or more p-type layers. The one or more p-type layers may include a p-type exciton blocking layer. The D-type exciton blocking layer may have a valence band closely matching the valence band of the photoactive layer (e.g., perovskite layer) of the solar cell. This may allow holes to be easily transported from the photoactive layer to the HTL.
The p-type layer may be made 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 the following: nickel oxide, thienyl, phenylethynyl, dithiazolyl, benzothiazolyl, diketopyrrolopyrrole, ethoxydithiothienyl, amino, triphenylamino, carbazolyl, ethylenedioxythienyl, dioxythienyl or fluorenyl. Additionally or alternatively, the D-form may comprise spiro-ome tad (2, 2', 7' -tetra- (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-methoxyaniline-4 ',4 "-diyl ], hexathiophene, 9, 10-bis (phenylethynyl) anthracene, 5, 12-bis (phenylethynyl) naphthacene, bisindenopylene, 9, 10-diphenylanthracene, PEDOT-TMA, PEDOT: PSS, perfluorinated pentacenes, perylenes, poly (p-phenylene ether), poly (p-phenylene sulfide), quinacridones, rubrene, 4- (dimethylamino) benzaldehyde diphenylhydrazones, 4- (benzhydrylamino) benzaldehyde-N, N-diphenylhydrazones or phthalocyanines.
Although described herein with respect to a silicon-perovskite stacked solar module, the methods and apparatus of the present disclosure may be used with any combination of solar cells having perovskite layers. For example, the tandem solar module may be a tandem CdTe-perovskite solar module. In another example, the tandem solar module may be a dye sensitized solar cell-perovskite solar cell module.
Fig. 1 schematically illustrates a stacked, 4-terminal, silicon-perovskite solar module 100 according to one embodiment of the disclosure. The solar module 100 can have a top glass sheet 105, a first TCO layer 110, an HTL 115, a perovskite layer 120, an ETL125, a second TCO layer 130, an encapsulant 135, silicon solar cells 140, and a backsheet 145.
The top glass sheet 105 may protect the underlying layers of the solar module 100 from dust and moisture. The top glass sheet 105 and solar module 100 as a whole may have a form factor corresponding to a conventional silicon solar panel. For example, the top glass sheet 105 may have a form factor of a silicon solar panel corresponding to 32 cells, 36 cells, 48 cells, 60 cells, 72 cells, 96 cells, or 144 cells. The top glass sheet 105 may have a thickness of at least about 2.0 millimeters (mm), 2.5mm, 3.0mm, 3.5mm, 4.0mm, 4.5mm, 5.0mm, or greater. The top glass sheet 105 may have a thickness of up to about 5.0mm, 4.5mm, 4.0mm, 3.5mm, 3.0mm, 2.5mm, 2.0mm, or less. The top glass plate 105 may be transparent to allow light to access the solar cells below. In some cases, the top surface of the top glass plate 105 may be covered with polydimethylsiloxane ("PDMS") (e.g., 1:10 alumina PDMS, textured 1:50 alumina PDMS, or textured PDMS), which may improve light trapping and index matching. In some cases, the top surface of the top glass sheet 105 may be covered with an anti-reflective coating. In some cases, the bottom surface of the top glass plate 105 may be textured to be able to scatter more light back into the perovskite layer 120.
Together, the first TCO layer 110, HTL 115, perovskite layer 120, ETL 125, and second TCO layer 130 may form a perovskite solar cell. The perovskite solar cell may be configured on the bottom surface of the top glass sheet 105 by the manufacturing method described with reference to fig. 3-10. The perovskite solar cell may have a higher bandgap than the silicon solar cell 140. For example, the number of the cells to be processed, the perovskite solar cell may have a band gap of about 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, 1.86, 1.85, 1.86, 1.92, 1.85, 1.98, 2.02, 2.05, 2.98, 2.02, 2.9, 2.7, 2.98, 2.05, 2.9, 2.75, 2.9, 2.05, 2.9, 2.75, 2.7, 2.75, 2.9, 2.75, 2.7, 2.75, or more. In contrast, the silicon solar cell may have a bandgap of about 1.1 eV. Thus, the perovskite solar cell may be capable of efficiently converting shorter wavelength light into electricity. The perovskite solar cell may be transparent to longer wavelength light, which may allow the underlying silicon solar cell to absorb such longer wavelength light and convert it into electricity. The perovskite solar cell and silicon solar cell together may be capable of efficiently converting a broader spectrum of light into electricity than a single solar cell.
The first TCO layer 110 may be disposed directly on the top glass plate 105. Depositing the first TCO layer 110 directly on the top glass plate 105 may prevent damage to the HTL 115 and the perovskite layer 120. The first TCO layer 110 may 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), 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 micron, or more. The first TCO layer 110 can have a thickness up to about 1 micron, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 200nm, 100nm, or less. The first TCO layer 110 may be made of Indium Tin Oxide (ITO). The first TCO layer 110 may be made of doped ITO. The TCO layer can 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 or greater. The TCO layer can have a resistance of up to 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 ohm/square or less.
The HTL 115 may be configured on the TCO layer 110. The HTL 115 may facilitate the transport of holes from the perovskite layer 120 to the first TCO layer 110 without compromising transparency and conductivity. Conversely, the HTL 115 may inhibit electron transport. In certain embodiments, the HTL 115 is made of one or more nickel oxide layers. In other embodiments, the HTL 115 is made of another suitable p-type material described in this disclosure. The HTL 115 may have a thickness of at least about 5nm, 10nm, 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 micron, or more. The HTL 115 may have a thickness of up to about 1 micron, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 200nm, 100nm, 50nm, 20nm, 10nm, 5nm, or less.
The perovskite layer 120 may be disposed on the HTL 115. The perovskite layer 120 may be a photoactive layer of the perovskite solar cell. That is, the perovskite layer 120 may absorb light and generate holes and electrons, which then diffuse into the HTL 115 and ETL 125, respectively. In certain embodiments, perovskite layer 120 is made of lead methyl ammonium tri-iodide, lead methyl ammonium tri-bromide, lead methyl ammonium tri-chloride, or any combination thereof. In other embodiments, the perovskite layer 120 is made of lead formamidine tri-iodide, lead formamidine tri-bromide, lead formamidine tri-chloride, or any combination thereof. In other embodiments, perovskite layer 120 is made of cesium lead triiodide, cesium lead tribromide, cesium lead trichloride, or any combination thereof. In certain embodiments, the perovskite layer may be a triple cationic perovskite material having different proportions of formamidine, methylammonium, and cesium cations. The incorporation of cesium into the perovskite lattice provides enhanced thermodynamic stability. The bandgap of perovskite layer 120 may be adjusted by adjusting the halide ion content of the lead methylammonium trihalide or lead formamidine trihalide. The perovskite layer 120 may have a thickness of at least about 250nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 micron, 1.25 microns, 1.5 microns, 1.75 microns, 2 microns, or more. The perovskite layer 120 may have a thickness of up to about 2 microns, 1.75 microns, 1.5 microns, 1.25 microns, 1 micron, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 250nm, or less.
The ETL 125 may be configured on the perovskite layer 120. The ETL 125 may facilitate electron transport from the perovskite layer 120 to the second TCO layer 130 without compromising transparency and conductivity. In contrast, ETL 115 may inhibit electron transport. In certain embodiments, the ETL 125 is made from phenyl-C61-butanoic acid methyl ester ("PCBM"). In other embodiments, the ETL 125 is made from another suitable n-type material (e.g., C60) described in this disclosure. The ETL 115 can have a thickness of at least about 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 200nm, 300nm, 400nm, 500nm, or more. The ETL 115 can have a thickness of up to about 500nm, 400nm, 300nm, 200nm, 100nm, 90nm, 80nm, 70nm, 60nm, 50nm, 40nm, 30nm, 20nm, 10nm, or less. The interface between the ETL and perovskite layer may be important to the performance of the perovskite layer. The surface of the perovskite layer may be hydrophilic in order to be able to well cover a hydrophilic ETL (e.g. PCBM). The combination of environment (e.g. < 15% low humidity, low temperature of 18 to 24 ℃) and solvent compatibility can affect the quality of the perovskite layer-ETL connection.
The second TCO layer 130 may be disposed on the ETL 125. The second TCO layer 130 may serve as the negative terminal or anode of the perovskite solar cell. The second TCO layer 130 can have a thickness of at least about 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 micron, or more. The second TCO layer 130 may have a thickness up to about 1 micron, 900nm, 800nm, 700nm, 600nm, 500nm, 400nm, 300nm, 200nm, 100nm, or less. The second TCO layer 110 may be made of indium oxide (ITO). The second TCO layer 110 may be made of doped ITO.
An encapsulant 135 can be disposed between the second TCO layer 130 of the perovskite solar cell and the silicon solar cell 140. The encapsulant 135 may prevent the perovskite solar cell and the silicon solar cell 140 from being exposed to dust and moisture. The encapsulant 135 may electrically insulate the perovskite solar cell from the silicon solar cell 140. The encapsulant 135 can have a high refractive index (e.g., a refractive index greater than 1.4) that matches the refractive indices of the TCO layer 130 of the perovskite solar cell and the top silicon nitride or TCO layer of the silicon solar cell 140. Such high refractive index materials may reduce transmission losses between the TCO layer 130, encapsulant 135, and silicon solar cell 140, resulting in an increase in the current density of the solar module 100. The use of high refractive index materials may also enhance light trapping. The high refractive index material may be ethylene vinyl acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, paraffin, or the like. Example 1 and fig. 9 described below illustrate the improvements achieved by using certain high refractive index materials in encapsulant 135. The encapsulant may be a TCO layer. For example, the TCO layer may cover the perovskite layer such that the TCO layer protects the perovskite layer from external conditions (e.g., water, oxygen, etc.). In this example, by using a TCO layer as an encapsulant, the reliability of the integrated stack module may be improved. The encapsulant may comprise ethylene vinyl acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, paraffin, and the like. The encapsulant layer may insulate both the perovskite solar cell and the silicon solar cell from the surrounding environment. For example, the encapsulant may encapsulate both the perovskite layer and the silicon layer simultaneously. The encapsulant layer may be configured to prevent volatilization of one or more components of the perovskite layer. For example, the encapsulant can minimize the loss of organic cations (e.g., methyl ammonium, formamidine, etc.) caused by the heating of the perovskite layer. In another example, the encapsulant may reduce the outflow of chemicals, such as lead iodide or other lead halides, from the perovskite layer, which may lead to reduced reliability of the integrated stack module. The encapsulant may be treated with sufficient cross-linking to protect the perovskite layer from the volatilization of water, oxygen, organic compounds of the perovskite layer, and the like, or any combination thereof. The encapsulant may have a percent crosslinking of at least about 50, 60, 70, 80, 90, 95% or more. The encapsulant may have a percent crosslinking of up to about 95, 90, 80, 70, 60, 50% or less.
In general, the silicon solar cell 140 may be a p-type silicon solar cell having a p-type substrate covered by a thin n-type layer ("emitter"), or it may be an n-type silicon solar cell having an n-type substrate covered by a thin p-type 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 interdigitated back contact cell (IBC), or the like.
The silicon solar cell 140 may have a back sheet 145. The back sheet 145 may seal the solar module 100 from moisture ingress. In some cases, the back plate 145 may be a glass plate having a top surface and a bottom surface. The top surface of the glass plate may have a highly reflective coating or textured surface to further enhance light trapping or scattering back into the silicon solar cell 140 and perovskite layer 120. The glass sheet may be transparent. The glass sheet may be substantially transparent. The transparency of the glass sheet may facilitate double sided operation of the solar cell. For example, the solar cell may be configured to absorb light from both sides of the solar cell.
The perovskite solar cell and the silicon solar cell 140 may be electrically insulated from each other, and each cell may have its own terminal. That is, the stacked solar module may be a 4-terminal module. The perovskite solar cell and the silicon solar cell 140 may be connected in series or in parallel by connecting the terminals in a suitable manner. In the case of a series connection, the perovskite solar cell and the silicon solar cell may be current matched. In case of parallel connection, the perovskite solar cell and the silicon solar cell may be voltage matched. The current matching or voltage matching may be achieved using laser scribing, for example by connecting individual scribed perovskite solar cells in series or parallel to achieve the desired voltage or current. The parallel or series connection between the perovskite solar cell and the silicon solar cell may be performed by bus bars/electrodes prior to module lamination. This allows for quick and easy introduction into any existing silicon manufacturing process.
The solar module 100 may have a power conversion efficiency of at least about 25%, 26%, 27%, 28%, 29%, 30%, or more.
Fig. 2 schematically illustrates how the perovskite layer 120 of fig. 1 may be formed. A metallic Pb layer may be deposited on the HTL by physical vapor deposition. Next, methyl Ammonium Iodide (MAI) or formamidine iodide (FAI) may be applied to the metal Pb layer. Finally, the MAI or FAI may be exposed to an iodine gas to form perovskite layer 120, which may be lead methyl ammonium tri-iodide or lead formamidine tri-iodide. This and other manufacturing processes will be described in more detail in subsequent figures.
TCO fabrication
The first TCO layer 110 and the second TCO layer 130 may serve as electrical contacts for the perovskite solar cell while maintaining the translucency of the perovskite solar cell such that the underlying silicon solar cell 140 may still absorb light. The first TCO layer 110 and the second TCO layer 130 may be fabricated using a Physical Vapor Deposition (PVD) process. The PVD process can be tuned such that the resulting TCO layer is transparent to light (e.g., 300 nanometers ("nm") to 1200nm 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 millitorr and the deposition power may be about 20 watts to about 100 watts. In addition, the thickness of the first TCO layer 110 and the second TCO layer 130 may be set to achieve this transparency. This transparency may allow the underlying silicon solar cell 140 to absorb as much light as possible that has not been absorbed by the perovskite layer 120, which perovskite layer 120 typically absorbs light having a wavelength of 300nm to 700 nm.
In the fabrication of the second TCO layer 130, the process may be prone to defects in the ETL 125 and perovskite layer 120 due to the ultraviolet light and plasma generated argon/oxygen ions during PVD. Such defects may reduce the performance of perovskite layer 120 as an electron-hole pair absorber. For example, as a result of such defects, perovskite layer 120 may exhibit a lower open circuit voltage and a lower fill factor. It may be beneficial to minimize the creation of such defects.
In one embodiment, the damage may be minimized by first creating a buffer layer of TCO on the ETL 125 by a low power PVD process. The power in the low power PVD process may be 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/square centimeter ("W/cm) 2 ") or lower. The buffer layer may have a thickness of at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65nm or more. The thickness of the buffer layer may be up to about 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5nm or less. The ultraviolet damage is typically created by high power ions that penetrate deep into the ETL 125 and the bulk of the perovskite layer 120, breaking or damaging molecular bonds, and causing a drop in both open circuit voltage and series resistance. Creating the buffer layer using low power PVD may block energetic ions in subsequent process steps from reaching the ETL 125 and perovskite layer 125.
The bulk layer of the TCO can be at most 1.00, 0.95, 0.90, 0.85, 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45W/cm 2 Or lower deposition energy is deposited on the buffer layer of the TCO.
In some cases, an ultra-thin silver layer may be deposited at the interface between the ETL 125 and the second TCO layer 130 by evaporation, sputtering, or atomic layer deposition. The ultra-thin silver layer 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 ultra-thin silver layer may act as a barrier to uv light or plasma during PVD of the second TCO layer 130. In some cases, the second TCO layer may be post-annealed to partially repair some damage caused by uv light or plasma during PVD. The post-annealing may be performed at 100-140 ℃ for 2 to 4 minutes.
The bulk layer of TCO can be at most 0.90, 0.85, 0.80, 0.75, 0.70, 0.65, 0.60, 0.55, 0.50, 0.45W/cm 2 Or lower deposition energy is deposited on the buffer layer of the TCO.
Conventionally, the above physical vapor deposition process may be performed in a compartment having a shutter disposed between a sputtering source and a target substrate. The shutter can be quickly actuated (i.e., opened and closed) to briefly space the target substrate from the sputter source. The abrupt nature of the shutter may cause damage to the sensitive perovskite and transport layer from ion impact and exposure to UV radiation. Furthermore, the entire target substrate is subjected to the entire sequence of TCO depositions, which may be several minutes long, to achieve a thickness on the order of 300-900nm to meet sheet resistance and transmission requirements. Thus, the physical vapor deposition process may inherently cause greater ion and UV damage to the target substrate than expected, which may create defects and recombination sites in the layer of the target substrate, degrading its electrical performance as an electron-hole pair absorber layer.
To address the shortcomings of conventional physical vapor deposition processes, the TCO layers 110 and 130 may instead be fabricated in an inline fabrication process. The inline fabrication process may be performed in a plurality of process compartments in which deposition of a selected target material occurs. A conveyor belt may transport the target substrate between the plurality of process compartments. The inline fabrication process may provide for deposition of a TCO layer while maintaining low resistivity, good transmittance, and uniform thickness of the perovskite solar cell. The inline manufacturing process may be a vertical or horizontal process. An example of a horizontal inline manufacturing system is shown in fig. 14.
The inline fabrication process may reduce defects in the ETL 125 and perovskite layer 120 due to argon/oxygen ions generated by ultraviolet light and plasma during TCO physical vapor deposition. The use of moving conveyor belts in multiple process compartments may reduce defects formed in the ETL 125 and perovskite layer 120. The multi-compartment system can minimize the amount of time the target substrate is exposed to plasma deposition. The target substrate may be exposed to deposition in only certain compartments. For example, the target substrate may not be exposed to deposition in the buffer compartment, while the target substrate is exposed to deposition in the process compartment where the first and second TCO layers are fabricated. In certain embodiments, a target substrate containing the top glass plate 105, the first TCO layer 110, the HTL 115, the perovskite layer 120, and the ETL 125 is loaded onto a conveyor belt of the inline PVD fabrication tool. The conveyor belt transports the target substrate into the target compartment such that the ETL layer 125 is TCO deposited facing the TCO source. Depending on the desired thickness and composition of the second TCO layer and the flux of the TCO source, there may be one or more target substrates simultaneously within the compartment, or there may be multiple compartments with a single target substrate. Each compartment may be separated by a door to minimize cross-contamination and minimize damage caused by plasma exposure. In some cases, the target substrate passes through a first deposition compartment to deposit a buffer layer of ITO. The substrate then passes through a buffer compartment and finally through a second deposition compartment to deposit a bulk layer of ITO. The buffer compartment may prevent cross-contamination between the first and second deposition compartments if, for example, the composition or deposition parameters of the two ITO layers are different.
To further reduce direct exposure to deposition, moving the target substrate on the conveyor ensures that each portion of the target substrate is directly exposed to deposition only as that portion of the target substrate moves through the deposition zone. The amount of time each portion of the target substrate is exposed to direct deposition depends on the speed of the conveyor belt. The speed of the conveyor belt can be adjusted to minimize the amount of time each portion of the substrate is exposed directly while still ensuring that each layer is adequately deposited on the target substrate. The moving conveyor belt provides a more gradual deposition profile on the target substrate, in contrast to the steeper profile created by conventional shutters.
The plurality of compartments may also include a shield or other blocking barrier between compartments to ensure that ions and UV exposure in other compartments are blocked when the target substrate enters a compartment where no deposition is present. The plurality of compartments may also contain a shield surrounding the deposition area to block ions and UV radiation from areas of the substrate that are not directly exposed to the deposition. Furthermore, the multi-compartment system allows TCO layer deposition with a uniform thickness and much lower plasma power without affecting the deposition duration.
In fabricating the second TCO layer, the inline fabrication process may also implement the techniques described above (e.g., optimizing process parameters such as gas flow/pressure, deposition power, thickness and materials, using buffer layers, reducing deposition energy, using ultra-thin silver layers, and using an annealing process) to further reduce defects formed in the ETL 125 and perovskite layer 120. The process limits the number of defects at the interface between the second TCO layer 130 and the ETL 125 and in both the ETL 125 and the bulk of the perovskite layer 120. Other examples of process parameters may include, but are not limited to, chemical formation parameters (e.g., solvent composition, presence or absence of additives, one-shot formulation, two-shot formulation, etc.), ultrasonic spray process parameters (e.g., spray volume, spray speed, ultrasonic power, substrate lateral speed, nozzle height, nozzle width, nozzle angle, environmental factors, humidity, atmospheric composition, temperature, etc.), post-coating process parameters (e.g., drying duration, rinse duration, external environmental parameters, solvent chemistry, annealing time, annealing temperature, etc.), transport layer coating parameters (e.g., coating type, surface conditions, layer thickness, layer conformality, etc.), etc., or any combination thereof.
Fig. 3 is a flow chart of a fabrication process 300 for forming a perovskite photovoltaic cell. Process 300 may optionally include creating a substrate (310) comprising a first transparent conductive layer and a hole transport layer. In some cases, a preformed substrate may instead be provided.
Fig. 4 is a flowchart of operation 310 of fig. 3. Operation 310 may include providing a substrate (311). The substrate may be a transparent substrate. The substrate may comprise a silicon-based glass (e.g., amorphous silica, doped silica, etc.), a transparent conductive oxide, a ceramic, a chalcogenide glass, a polymer (e.g., transparent plastic, polymethyl methacrylate, etc.), etc., or any combination thereof. The substrate may comprise a top surface of a solar module. For example, the substrate may be a top glass of a silicon solar panel assembly. The substrate may be textured and/or patterned. For example, the substrate may include nanoscale textures configured as an anti-reflective coating and an adherent surface. In another example, the substrate may include a patterning configured to create a photonic channel. In another example, the substrate may include a pre-patterned portion (e.g., a top contact grid layout) with electrodes for removing energy from the solar cell. The substrate can have an area 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 square meters, or more. The substrate may have an area of up to about 25, 20, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1 square meters, or less. The substrate may be a large format substrate. For example, the substrate may be a 10 th generation substrate.
Operation 310 may include applying one or more first transparent conductive materials to the substrate to form a first transparent conductive layer (312). 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-dioctylcyclopentathiophene), etc.), a carbon nanotube, graphene, a nanowire (e.g., silver nanowire), a metal grid (e.g., a metal-containing grid contact), a film (e.g., a metal film), a conductive grain boundary, etc., or any combination thereof. The transparent conductive layer can have a full spectral transparency of at least about 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.9% or more. The transparent conductive layer can have a full spectral transparency of up to about 99.9%, 99%, 98%, 97%, 96%, 95%, 90%, 85%, 80%, 75%, 70%, 60%, 50%, 40%, 30%, 20% or less. The transparent conductive layer may have a full spectral transparency within a range defined by any two of the above values. For example, the transparent conductive layer may have a full spectral transparency of 75% to 85%. The transparent conductive layer can have a transparency over the spectral band of at least about 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.9% or greater. The transparent conductive layer can have a transparency over the spectral band of up to about 99.9%, 99%, 98%, 97%, 96%, 95%, 90%, 85%, 80%, 75%, 70%, 60%, 50%, 40%, 30%, 20% or less. For example, the transparent conductive layer may have a transmittance of 85% in a wavelength range of 400nm to 1200 nm. The transparent conductive layer may serve as a barrier to the perovskite layer from moisture, gases, dust, etc. The transparent conductive layer may also prevent diffusion of ions (e.g., metal ions) that may affect the performance of the perovskite layer. Methods of forming transparent conductive oxide layers are described elsewhere herein. For example, the transparent conductive oxide layer may be formed using PVD and/or inline fabrication processes described herein.
Operation 310 may include applying one or more hole transport layers (313) to the transparent conductive layer. The one or more hole transport layers may be configured to shuttle holes from the absorber layer to the transparent conductive layer and away from the solar module. The one or more hole transport layers may comprise organic molecules (e.g., 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino)]9,9' -spirobifluorene (Spiro-OMeTAD)), inorganic oxides (e.g. nickel oxide (NiO) x ) Copper oxide (CuO) x ) Cobalt oxide (CoO) x ) Chromium oxide (CrO) x ) Vanadium Oxide (VO) x ) Tungsten oxide (WO) x ) Molybdenum oxide (MoO) x ) Copper aluminum oxide (CuAlO) 2 ) Copper chromium oxide (CuCrO) 2 ) Copper gallium oxide (CuGaO) 2 ) Etc.), inorganic chalcogenides (e.g., copper iodide (CuI), copper indium sulfide (CuInS) 2 ) Copper zinc tin sulfide (CuZnSnS) 4 ) Copper barium tin sulfide (CuBaSnS) 4 ) Etc.), other inorganic materials (e.g., copper thiocyanate (CuSCN), etc.), organic polymers, etc., or any combination thereof. For example, a glass substrate covered in indium tin oxide may be coated with nickel oxide to form a hole transport layer on the transparent conductive layer.
Operation 310 may optionally include performing one or more photolithography operations on the hole transport layer (314). The one or more lithographic 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 writing processes (e.g., dip pen lithography, inkjet printing), etc., or any combination thereof. For example, a plurality of features may be etched on the hole transport layer using laser scribing. The one or more lithographic operations may include the addition and/or subtraction of features. For example, the features may be cured and permanently set. In another example, features may be formed by removing material from a target.
Returning to fig. 3, process 300 may include applying one or more perovskite precursors to the hole transport layer (320). The applying may include 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, electroplating, physical vapor deposition, thermal evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, cathodic arc deposition, ultrasonic spraying, inkjet printing, and the like, or any combination thereof. The applying may comprise applying a single perovskite precursor at a time. For example, a first perovskite precursor may be evaporated onto the hole transport layer, and a second perovskite precursor may be subsequently sprayed onto the first precursor. The applying may include applying multiple precursors at one time. For example, an inkjet printer may apply a solution containing multiple precursors. Process 300 may optionally include applying one or more additional perovskite precursors to the hole transport layer (330). The additional perovskite layer may be applied in the same manner as in operation 320. For example, the first precursor may be deposited by physical vapor deposition followed by deposition of the second precursor by physical vapor deposition. Alternatively, the additional perovskite layer may be applied in a different manner than in operation 320. For example, the first perovskite precursor may be deposited by physical vapor deposition, while the second perovskite precursor may be deposited by ultrasonic spraying. Operation 330 may be repeated a plurality of times. For example, a variety of additional perovskite precursors may be applied to the hole transport layer in a variety of operations.
Ultrasonic spray application may include the use of multiple nozzles. The ultrasonic spray process may include the use of a single nozzle. For example, the single nozzle may be configured to be rasterized over an application area to provide coverage of the area. In order to form a predetermined uniformity and/or thickness of a film deposited through the nozzle, a plurality of different types of nozzles may be tested, and an optimal nozzle may be selected from the plurality of different types of nozzles. Once the optimal nozzle is selected, a plurality of nozzles of this type may be used in ultrasonic spray application. The plurality of nozzles may form a nozzle set configured for spraying over a large area to increase throughput and efficiency. The nozzle groups may be nozzle strips (e.g., a row of nozzles in a single dimension), two-dimensionally arranged nozzles (e.g., nozzles distributed over a rectangular shape), three-dimensionally arranged nozzles (e.g., a plurality of nozzles distributed in three dimensions). The nozzle may be adjusted to dispense at an angle. The angle 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 degrees or more from parallel to the substrate. The angle may be offset from parallel lines to the substrate by up to about 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 degrees or less. The angle may be configured to reduce or eliminate precursor misplacement of the substrate and contamination of other components of the manufacturing process. Roll-to-roll inline manufacturing processes may be achieved using ultrasonic spray application. In the roll-to-roll inline manufacturing process, a series of nozzle groups may each sequentially add different layers to a substrate, the substrate may be processed (e.g., annealed, laser scribed, etc.), and finished photovoltaic cells may be produced on a single production line. The use of a roll-to-roll process may result in significant improvements in production costs and speed over a stepwise manufacturing process.
The 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 halides, tin halides, metal oxides, metal halides, etc.), organic halides (e.g., formamidines, methyl ammonium chloride, methyl ammonium bromide, methyl ammonium iodide, butyl ammonium halides, 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. A variety of perovskite precursors may be used as the one or more perovskite precursors. For example, both methyl ammonium iodide and butyl ammonium iodide may be used as perovskite precursors. In this example, the ratio of methyl ammonium iodide to butyl ammonium iodide may be about 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 may be used as part of the perovskite precursor. The use of different mixtures of lead halides may allow the band gap of the perovskite layer to be tuned. For example, different bandgaps can be created using different mixtures of lead (II) bromide and lead (II) iodide. The use of varying amounts of lead (II) chloride can affect the crystal stability of the perovskite layer and can prevent phase separation within the layer. The amount of added lead (II) chloride may be greater than the amount of added lead (II) bromide by weight. The amount of added lead (II) chloride may be less than the amount of added lead (II) bromide by weight. The amount of lead (II) chloride added may be the same as the amount of lead (II) bromide added by weight. The amount of lead (II) iodide soluble in the solution may be related to the amounts of lead (II) bromide and lead (II) chloride in the solution. For example, adding more lead (II) bromide and lead (II) chloride to the lead (II) iodide solution may increase the solubility of lead (II) iodide and result in a reduction of particles in the perovskite layer.
The one or more perovskite precursors may be one or more perovskite precursor solutions. For example, the lead (II) iodide solution in the dimethyl sulfoxide solution may be a perovskite precursor. The perovskite precursor may be 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 perovskite precursor solution. The perovskite precursor may be 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, 0.1 wt% or less perovskite precursor solution. The solution may comprise one or more solvents. Examples of solvents include, but are not limited to, polar solvents (e.g., water, dimethyl sulfoxide, dimethylformamide, ethers, esters, acetates, acetone, etc.), non-polar solvents (e.g., hexane, toluene, etc.), and the like, or any combination thereof. Proper mixing of the solvent and solvent composition can facilitate controlled solvent removal rates, thereby affecting grain development and formation of bulk defects. Adjusting the interaction of the coordination strength of the solvent and the evaporation rate of the precursor solution allows for better control of the perovskite film formed and the kinetics of the reaction of said formation. For example, a weakly coordinating solvent that evaporates rapidly may form a more disordered film, but may also result in less residual solvent being present in the film. The mixture of solvents may increase solute solubility, decrease evaporation rates, increase performance of the application method, and the like. For example, a combination of NMP and DMSO may increase solute solubility and decrease solvent evaporation rate. In this example, the nature of the NMO/DMSO mixture can reduce premature crystallization of the perovskite and improve film quality. In another example, adding NMP to DMF may increase the spray width of the solution through an ultrasonic spray apparatus, which may provide greater flexibility in the spray parameters used.
The one or more perovskite precursors may comprise one or more additives. The addition of the one or more additives may be configured to reduce and/or eliminate defects in the perovskite layer prepared elsewhere herein. The one or more additives may include one or more recrystallization solvents. The one or more recrystallization solvents may be added to a solution comprising the one or more perovskite precursors. The one or more recrystallization solvents may be applied after deposition of the one or more perovskite precursors and/or after annealing of the one or more perovskite precursors. For example, a lead halide precursor may be applied followed by a recrystallization solvent, and the perovskite precursor may be further annealed to orient the lead halide precursor for better integration of the methyl ammonium iodide. Examples of recrystallization solvents include, but are not limited to, halogenated benzenes (e.g., chlorobenzene, bromobenzene, etc.), haloforms (e.g., chloroform, iodoform, etc.), ethers (e.g., diethyl ether), etc., or any combination thereof.
Various parameters may be adjusted to provide a predetermined perovskite layer. Examples of parameters include, but are not limited to, perovskite precursor solution application temperature, volume application rate, ultrasonic power of an ultrasonic spray apparatus, lateral speed of precursor application (e.g., speed of substrate movement through the applicator), applicator height (e.g., distance from the applicator to the substrate), environmental factors (e.g., humidity, reactive gas content, temperature, etc.), wetted surface energy, etc., or any combination thereof. Any portion of process 300, including the application of perovskite precursors, may be performed 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%, 99% or more. The controlled environment may have a relative humidity of up to about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or less. The controlled environment may comprise a controlled atmosphere. The controlled atmosphere may include an inert gas (e.g., nitrogen, inert gas, etc.). The controlled atmosphere may have an oxygen content of at least about 1 parts per million (ppm), 10ppm, 50ppm, 100ppm, 500ppm, 1, 000ppm, 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, 000ppm, 1, 000pm, 500ppm, 100ppm, 50ppm, 10ppm, 1ppm or less. The controlled atmosphere may be 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 more. The controlled atmosphere may be at a temperature of up to about 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 less.
Process 300 may include performing one or more processing operations on the perovskite precursor to produce a perovskite layer (340). Operation 340 may be omitted if the perovskite precursor is instead deposited as a complete perovskite layer. Fig. 5 is a flowchart of operation 340 of fig. 3. Operation 340 may include providing a substrate comprising a first transparent conductive layer, a hole transport layer, and one or more applied perovskite precursors (341). The substrate may be the result of operations 310-330 of process 300.
Operation 340 may include performing one or more processing operations on the perovskite precursor to produce a perovskite layer (342). The one or more processing operations may include annealing, exposure (e.g., ultraviolet light exposure), agitation (e.g., vibration), functionalization (e.g., surface functionalization), electroplating, template reversal, 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 another example, the perovskite precursor may be annealed and subsequently functionalized. The annealing may be under an inert atmosphere (e.g., argon atmosphere, nitrogen atmosphere). The annealing may be performed under a reactive atmosphere, such as an atmosphere comprising a reagent (e.g., methyl ammonium). The annealing may 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 ℃ or more. The annealing may be performed at a temperature of up to about 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 less. The annealing may be performed at a temperature range defined by any two of the above values. For example, the annealing may be performed at a temperature of 90 to 120 ℃. The annealing may be performed for a period of 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. The annealing may be performed for a time of up to about 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, 0.5 minutes or less. The annealing may be performed for a time frame defined by either of the above values. For example, the annealing may be performed for a time period of about 5 to about 15 minutes. There may be multiple annealing processes applied to the substrate. For example, the substrate may be annealed at a first time and temperature, followed by a second time and temperature. Such additional annealing processes may reduce the number of defects present in the perovskite layer and improve performance.
Operation 340 may include applying one or more additional layers to the perovskite layer (343). 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 further layers may comprise one or more further perovskite precursors. For example, an iodine gas may be applied to form an iodine layer on the perovskite and/or perovskite precursor layer. The one or more additional layers may include one or more cleaning operations. The cleaning operation 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, and the like. The one or more additional layers may include one or more passivation layers. The passivation layer may contain an agent configured to passivate and/or stabilize the perovskite layer. For example, the application of a solution comprising phenethyl ammonium iodide may passivate and stabilize the grains of the perovskite layer.
Operation 340 may include performing one or more lithographic operations on the one or more additional layers and/or perovskite layers (344). The one or more lithographic operations may be one or more lithographic operations described elsewhere herein. For example, laser scribing may be used to create features on a perovskite layer.
Returning to fig. 3, process 300 may include applying an electron transport layer (350) to the perovskite layer. Fig. 6 is a flowchart of operation 350 of fig. 3. Operation 350 may include providing a substrate (351) comprising a first transparent conductive layer, a hole transport layer, and a perovskite layer. The substrate may be the substrate produced by operations 310-340 of fig. 3.
Operation 350 may include applying an electron transport layer (352) to the perovskite layer. By a means ofThe electron transport layer may be applied by methods and systems described elsewhere herein (e.g., physical vapor deposition, ultrasonic spraying, etc.). The electron transport layer may comprise a material having a conduction band minimum that is smaller than the perovskite layer. For example, if the perovskite layer has a conduction band minimum of-3.9 eV, the electron transport layer may have a conduction band minimum of-4 eV. Examples of electron transport layer materials include, but are not limited to, titanium oxides (e.g., tiO 2 ) 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-methyl butyrate (PCBM), poly (3-hexylthiophene-2, 5-diyl) (P3 HT), etc.), lithium fluoride, buckminsterfullerenes (C60), etc., or any combination thereof. Operation 350 may optionally include performing one or more lithographic operations on the electron transport layer (353). The one or more lithographic operations may be one or more lithographic operations described elsewhere herein. For example, laser scribing may be used to create features on the electron transport layer.
Returning to fig. 3, process 300 may include applying a second transparent conductive layer (360) to the electron transport layer. Fig. 7 is a flowchart of operation 360 of fig. 3. Operation 360 may include providing a substrate (371) including 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.
Operation 360 may include applying a second transparent conductive layer (362) 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 than the first transparent conductive layer. The second transparent conductive layer may be deposited as described elsewhere herein (e.g., physical vapor deposition, etc.).
Operation 360 may include applying one or more bus bars (363) to the second transparent conductive layer. The one or more bus bars may be applied as bus bars (e.g., a pre-formed bus bar is applied to the second transparent conductive layer). For example, the bus bars may be formed from an evaporation process using a mask. The one or more bus bars may be applied as a solid film and subsequently formed into bus bars. For example, a silver film may be deposited onto the second transparent conductive layer and etched to form the bus bars. In another example, the bus bars may be formed from a silver film using laser scribing. Operation 360 may optionally include performing one or more lithographic operations (364) on the electron transport layer. The one or more lithographic operations may be one or more of the lithographic operations described elsewhere herein. For example, laser scribing may be used to create features on the second transparent conductive layer. The bus bar may be attached to at least about 2, 3, 4 or more terminals. The bus bar may be attached to up to about 4, 3, 2 or fewer terminals. The terminals may be configured to form a parallel connection with one or more further photovoltaic modules. The terminals may be configured to form a series connection with one or more further photovoltaic modules. The terminals may be scribed (e.g., laser scribed). The terminal may be configured to enable connection of the perovskite photovoltaic device prior to lamination with another photovoltaic device. For example, a perovskite photovoltaic device may be connected to a silicon photovoltaic device through two terminals.
Returning to fig. 3, process 300 may include applying an encapsulant (370) to the second transparent conductive layer. The encapsulant may be configured to reduce or substantially eliminate 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. Examples of encapsulants include, but are not limited to, polymers (e.g., butyl rubber, polymethyl methacrylate, polycarbonate, polyethylene, polystyrene, thermoplastic olefins, polypropylene, etc.), waxes (e.g., paraffin wax), metals (e.g., iron, copper), semiconductors (e.g., wide band gap semiconductors (e.g., zinc oxide, titanium oxide)), and the like, or any combination thereof.
The encapsulant may be applied over the second transparent conductive layer (e.g., over the entire layer), over a portion of the second transparent conductive layer (e.g., over a portion of the layer), over an edge of the second transparent conductive layer (e.g., as a seal over the entire layer stack), etc., or any combination thereof. For example, the encapsulant may be applied to the edges of the entire layer stack to prevent moisture and oxygen from diffusing into the stack. The encapsulant may be applied to the first conductive layer and the second conductive layer. For example, the substrate may include an encapsulant between the substrate and the first conductive layer. Example 3 below describes the use of PDMS as an encapsulant. Other examples of encapsulants include, but are not limited to, helioSeal TM Silica gel, butyl sealant, and the like. For edge encapsulation, the encapsulant may include tape. The tape may be a back adhesive barrier. The encapsulant may be placed such that the encapsulant end is 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 or more from the edge. The encapsulant may be placed such that the encapsulant end is at most 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.
After operation 370, the completed stack (e.g., substrate, perovskite layer, and other layers) may be used as a front panel for other photovoltaic modules. For example, the completed stack may be configured as a front junction of a dual junction photovoltaic module. The completed stack may be configured to serve as a substrate for other stacks. For example, the stack may be used as an initial substrate for the growth of silicon photovoltaic modules. The stack may be laminated to a second photovoltaic cell. The stack may 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 more. The stack may be laminated at a temperature of up to about 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 less.
Fig. 13 is a flow chart of a manufacturing process 1300 for forming a perovskite layer. Process 1300 may be one embodiment of operations 320-340 of fig. 3. Process 1300 may include providing a substrate including a hole transport layer (1310). The substrate may also include a transparent conductive layer as described elsewhere herein. The hole transport layer may be a hole transport layer as described elsewhere herein. The substrate may be a substrate as described elsewhere herein.
Process 1300 may include applying a lead layer to the hole transport layer (1320). The lead layer may comprise lead metal (e.g., lead (0)), lead salts (e.g., lead (II) acetate, lead (II) halides, lead (I) salts, etc.), or any combination thereof. For example, a metallic lead layer may be deposited on the hole transport layer, and a lead (II) acetate layer may be applied to the lead layer. The lead layer may be deposited as described elsewhere herein. For example, 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, the same physical vapor deposition apparatus may be used to deposit both the hole transport layer and the lead layer.
Process 1300 can include applying an organic halide salt layer (1330) to the lead layer. The organic halide may be an organic halide as described elsewhere herein. For example, a mixture of methyl ammonium iodide, methyl ammonium chloride, and formamidine may be applied to the lead layer. The organic halide layer may be applied by a deposition process as described elsewhere herein. For example, the organic halide may be applied by a spin coating process, an ultrasonic spray coating process, or the like.
Process 1300 may include applying a halide layer (1340) to the organic halide layer. The halide layer may comprise halides (e.g., fluorine, chlorine, bromine, iodine, etc.), oxyhalides (e.g., chlorate, etc.), other halide-containing compounds, etc., or any combination thereof. For example, the halide layer may include iodine. In another example, the halide layer may be iodine. The halide layer may be applied to the organic halide salt layer by a deposition process described elsewhere herein. 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 uniformly applied on the surface of the organic halide salt layer. In order to apply the halide uniformly, various different application devices may be used. 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 showerhead for application of perovskite precursors can be found in fig. 9. Another example of an application device may be a rod comprising one or more nozzles, which may translate across the surface of the substrate. For example, a rod of the same width as the substrate may be moved across the substrate to deposit a uniform halide coating.
Process 1300 may include performing one or more processing operations to form a perovskite layer (1350). The perovskite layer may be a perovskite layer as described elsewhere herein (e.g., the perovskite layer of fig. 3). The one or more processing operations may be one or more of the processing operations described elsewhere herein. For example, the lead layer with the lead acetate layer deposited atop, the methyl ammonium iodide/formamidine layer, and the iodide layer may be annealed together at a temperature of 90-120 ℃ to form a methyl ammonium iodide/formamidine lead perovskite layer. The one or more processing operations may include cleaning. The washing may include the use of one or more solvents as described elsewhere herein. The cleaning may be configured to remove unreacted precursor from the perovskite layer. For example, an isopropanol wash may be performed to remove residual organic halide salts. The one or more processing operations may include one or more processes. Examples of treatments include, but are not limited to, application of phenethyl ammonium iodide, thiocyanate cleaning, other passivation and/or stabilization processes, and the like, or any combination thereof.
In another aspect, the invention provides a method of producing a perovskite layer, the method comprising spraying a solution comprising a perovskite layer precursor. A quenching solution may be applied to the precursor to form a perovskite layer. The solution may contain all precursors of the perovskite layer. For example, the solution may comprise lead halides, organic halides, and halides. The solution may comprise a perovskite precursor as described elsewhere herein. The solution may be applied by the methods described elsewhere herein. For example, the solution may be applied by ultrasonic spray techniques. The solution may be treated after application. For example, the solution may be heated to remove solvent from the solution. The solution may be left untreated after application. The quenching solution may be applied to a solution (e.g., a precursor solution). The quenching solution may be applied to the dried precursor. The quenching solution may comprise an antisolvent (e.g., a solvent in which the perovskite precursor is more insoluble than in the solvent of the precursor solution). Examples of antisolvents include, but are not limited to, polar solvents (e.g., alcohols, acetone, etc.), long chain nonpolar solvents (e.g., octadecene, squalene, etc.), etc., or any combination thereof. The quenching solution may be applied as described elsewhere herein. For example, the quenching solution may be applied by ultrasonic spray techniques. The solution may be subjected to one or more atmospheric conditions to aid in the removal of the solvent. The one or more atmospheric conditions may include reduced pressure (e.g., applying a vacuum), increased pressure (e.g., purging a gas over the substrate), and the like, or combinations thereof. The depressurizing may include applying a partial vacuum around the substrate. This vacuum can draw solvent from the membrane to achieve rapid solvent removal and produce a high quality membrane. The pressurizing may include the use of an air knife or similar purging scheme to aid in the removal of solvent. Such high quality films may appear mirror-like under visual inspection. After the precursor solution is applied, the solution may be allowed to self-level for a period of time prior to curing. For example, the precursor solution may be allowed to stand on the substrate for a sufficient time to level before the solvent is removed and the perovskite layer is prepared.
Fig. 8 schematically illustrates perovskite precursor deposition compartments. Gas may flow from inlet 801 into compartment 802. The gas may be an inert gas (e.g., nitrogen, argon, etc.). The compartment 802 may contain one or more perovskite precursors. For example, the compartments may contain solid iodine. In another example, the compartment may contain liquid bromine. The gas may be configured to act as a carrier gas for one or more perovskite precursors in the reservoir. For example, the gas may carry sublimated iodine out of the zone. The compartment may contain an optical sensor assembly 803. The optical sensor assembly may include a light source and a detector as described elsewhere herein. For example, the optical sensor assembly may include a green laser and a photodiode detector. The gas may pick up the one or more perovskite precursors from the compartment 802 and flow into the compartment 804. The compartment 804 may be configured to regulate the flow of the gas and/or one or more perovskite precursors from the compartment 802. The compartments may be configured to prevent flow out of the deposition compartment 806. The compartment 804 may be configured as a bubbler (e.g., a water bubbler, a mercury bubbler, etc.), a mass flow controller (e.g., an iodine mass flow controller, etc.), or the like, or any combination thereof. The gas may flow from compartment 804 to compartment 806 through additional optical sensor assembly 805. The optical sensor assembly 805 may include a light source and a detector as described elsewhere herein. For example, the optical sensor assembly may include a green laser and a photodiode detector. The compartments may be as described elsewhere herein. For example, the compartments may be the compartments depicted in fig. 9. The compartment 808 may be made of or coated with a material that is resistant to halide gases. For example, the compartments may be made of titanium. In another example, the compartments may comprise an inert polymer coating. In another example, the compartments are made of glass. The compartments may be connected to an exhaust port 807, which exhaust port 807 may in turn be connected to a compartment 808. The compartment 808 may contain a bubbler. The compartment 808 may contain condenser equipment (e.g., cold head, cold clarifier, cold coil, etc.). The compartment 808 may be configured to prevent the one or more perovskite precursors from exiting the compartment 806 and entering the downstream environment. For example, the coldhead may condense iodine gas to prevent its emission into the atmosphere.
Fig. 9 schematically illustrates a shower head design for a spray nozzle. Gas may flow into the deposition compartment 903 through the inlet 901 through the nozzle 902. 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, 1000, or more holes. The plurality of holes may be up to about 1000, 750, 500, 250, 200, 150, 100, 75, 50, 25, 10, 5, 3, or less holes. The plurality of holes may be configured to uniformly distribute gas from the inlet 901 to the substrate 905 within the compartment 903. The substrate may be a substrate as described elsewhere herein. The substrate may be placed on the heater 906. The heater may be configured to anneal the substrate. For example, the heater may anneal the substrate to allow the reaction of perovskite precursors to form the perovskite layer. The compartment 903 may contain one or more exhaust ports 907. The exhaust port may be configured to remove excess gas (e.g., excess reactant, oxygen, water, etc.) from the atmosphere of the compartment. The compartment may contain a light source 908 directed toward a photodetector 909. The light source may include a laser (e.g., green laser), an incoherent light source (e.g., light emitting diode, etc.), or the like, or any combination thereof. The photodetectors may include zero-dimensional (OD) detectors (e.g., photodiodes), one-dimensional (1D) detectors (e.g., bar detectors), two-dimensional (2D) detectors (e.g., array detectors), thin film detectors (e.g., detectors using silver halide crystals on a thin film), phosphor plate detectors (e.g., plates of down-converting or down-converting phosphors), semiconductor detectors (e.g., semiconductor charge-coupled devices (CCDs), complementary Metal Oxide Semiconductor (CMOS) devices), and the like, or any combination thereof. The substrate may be loaded into an oven for an annealing process. For example, the substrate may be loaded into an oven with a plurality of other substrates by an auto loader to perform a batch annealing process.
Fig. 20 is a flow chart of a process 2000 for manufacturing a stacked solar module according to some embodiments of the present disclosure. The method may include providing a silicon solar panel (2010). The silicon solar panel may be as described elsewhere herein. For example, the silicon solar panel may be a front contact solar panel, an integrated back contact solar panel, a roof solar panel, or the like. The silicon solar 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. The silicon solar panel may have up to about 96, 95, 90, 85, 80, 75, 72, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 or less solar cells. In certain embodiments, the silicon solar panel has 60 six inch solar cells arranged in a 6 by 10 grid. The cells may be connected in series. The cells may each have an open circuit voltage of 0.7V, with a total open circuit voltage of about 42V.
The method may further include fabricating a perovskite on glass (2020) as described elsewhere herein. 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, 2 or fewer layers.
The method may further include laser scribing the perovskite on the glass to form perovskite cells or strips (2030). The manufacturing may include using manufacturing techniques described elsewhere herein. For example, the fabricating may include using laser scribing to define the one or more perovskite solar cells. The one or more perovskite solar cells may be a plurality of perovskite solar cells. The 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. The one or more perovskite solar cells may be 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, or less perovskite solar cells. The plurality of perovskite solar cells may be connected in series. The plurality of perovskite solar cells may be connected in parallel. The laser scribing may separate the perovskite layer into a plurality of segments. The plurality of segments may be formed as a plurality of perovskite solar cells. For example, contacts may be applied to the plurality of segments to extract charge from the plurality of segments.
The laser scribe may be configured to produce a plurality of perovskite cells that when connected together have the same or substantially the same voltage output as the silicon module. The voltage output per unit area of the perovskite layer may be known and the perovskite layer may be scribed to form a perovskite cell of sufficient size to provide a predetermined voltage. For example, the perovskite layer may be scribed to form 5 perovskite sub-modules, each sub-module containing 40 perovskite solar cells to match a silicon solar module having the same voltage output as the 40 perovskite solar cells. In this example, the 5 perovskite sub-modules may be connected in parallel to increase the current produced by the perovskite layer while maintaining a voltage match to the silicon module.
The method may further include connecting a cell of the silicon solar panel to the perovskite solar cell to form a stacked module (2040). The silicon solar panel and perovskite solar cell may employ a voltage matching configuration. The voltage matching configuration may be as described elsewhere herein. 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 cell may be connected such that there are a plurality of modules in the perovskite layer. For example, the rows of perovskite solar cells may each be connected in series, and the connected rows may be connected in parallel. The silicon solar panel and perovskite solar panel may be connected as described elsewhere herein. For example, the perovskite solar cell may be connected to the same junction box as the silicon solar cell by copper (or another metal, charge collection tape, etc.) terminals.
The method may also include encapsulating the module (2050). The encapsulation may include applying an encapsulant as described elsewhere herein. For example, the encapsulation may include applying a thermoplastic polyolefin to the perovskite layer. In another example, the encapsulation may include the use of a transparent conductive oxide.
The method may include applying a plurality of contacts to the one or more perovskite solar cells to electrically couple the one or more perovskite solar cells. The plurality of contacts may be applied using one or more of the processes described elsewhere herein. For example, the plurality of contacts may be evaporated onto the perovskite solar cell. In another example, the plurality of contacts may be lithographically applied to the perovskite solar cell. The method may include applying an encapsulant to the one or more perovskite solar cells. The application may be as described elsewhere herein. For example, the encapsulant may be applied by evaporation. In another example, the encapsulant may be spread as a viscous solution over the perovskite solar cell. The encapsulant may be as described elsewhere herein. For example, the encapsulant may be a thermoplastic polyolefin. The method may include applying an edge seal to the one or more perovskite solar cells. The edge seal may be as described elsewhere herein. For example, the edge seal may be Helioseal TM 。
The silicon solar panel and perovskite solar panel may be electrically coupled to the same junction box. Such coupling to the same junction box may allow for simple integration of the perovskite layer in existing silicon solar modules. Such coupling may also provide for simple installation of the stacked solar module, as there may be a single output from the stacked module rather than multiple outputs.
Fig. 16-19 show examples of different electrical network connections for different types of silicon-perovskite hybrid solar modules. The hybrid silicon-perovskite solar module may be as described elsewhere herein. Fig. 16 shows an example of front and back sides 1601 and 1602 and perovskite top module 1603 of a silicon solar module. The silicon solar module may include a front bus 1604. The front bus bar may be configured to connect each solar cell in the module to a single junction box output 1605. The silicon solar module may include terminals 1606. The terminals may comprise copper, silver, gold, iron, alloys thereof, charge collection tape, or the like, or any combination thereof. The terminals may be configured for electrical connection with the perovskite top module 1603. For example, the terminals may be configured to electrically connect the perovskite top module to a junction box. The terminals may be configured to provide a parallel connection between the silicon solar module and a perovskite top module. Alternatively, the terminals may be configured to provide a series connection between the silicon solar module and a perovskite top module. The stacked solar module may comprise a silicon solar panel. The silicon solar panel may include a plurality of silicon solar cells. The silicon solar panel may comprise a top glass sheet. The plurality of silicon solar panels may be connected in series and have a first open circuit voltage. The laminated solar module may include a perovskite solar panel disposed on a bottom surface of a top glass sheet of the silicon solar panel. The perovskite solar panel may comprise a plurality of segments. Each of the plurality of segments may comprise a plurality of laser-scribed perovskite strips. The plurality of laser scribed perovskite strips within the segment may be connected in series to produce a second open circuit voltage that is substantially the same as the first open circuit voltage. The stacked solar module may include an interconnect connecting the plurality of silicon solar cells and the plurality of sections of the perovskite solar panel in parallel.
The plurality of segments may comprise 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. The plurality of segments may comprise up to about 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, 2, or less segments. The plurality of segments may comprise a number of segments within a range defined by any two of the above values. For example, the plurality of segments may comprise from about 10 to about 200 segments.
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 herein. For example, the channels may be cut with laser scribing. The channels may be configured to isolate different perovskite solar cells from each other. In this way, a plurality of perovskite solar cells may be formed in the perovskite top module. Other channels perpendicular to the channels may be used to form a grid of solar cells. For example, a 5 by 40 array of perovskite solar panels may be formed from the perovskite layer. The perovskite top module may comprise 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 comprise up to about 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 less perovskite solar cells. For example, the perovskite top layer may contain 40 solar cells separated by channels. The perovskite solar cell may have a width of 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 or more. The perovskite solar cell may have a width of 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 or less. The perovskite solar cell may have a length of 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 perovskite solar cell may have a length of 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 ribbon (e.g. a solar cell spanning at most the length of the 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. Similarly, fig. 17 shows an example of a stacked perovskite-silicon solar module. The silicon solar panel may be a top contact solar panel. For example, the silicon solar panel may contain electrical contacts configured to extract power from the panel on the side of the silicon solar cell facing the sun. The module may contain one or more encapsulant layers 1701. The one or more encapsulant layers may be as described elsewhere herein. The one or more encapsulant layers may be applied to a substrate, and then the solar cells of the silicon solar module may be arranged on the one or more encapsulant layers. An additional encapsulant layer may be applied over the silicon solar cell, and then the perovskite on glass may be applied to the encapsulant layer. The encapsulant layer may be configured to allow electrical connection between the silicon layer and perovskite layer. Fig. 18 shows an example of a perovskite top module electrically connected with 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 contain electrical contacts configured to extract power from a panel located on the back side of the silicon solar cell. Fig. 19 shows an example of a perovskite top module electrically connected with a roof silicon solar module. The silicon solar panel may be a roof solar panel. For example, a plurality of silicon solar cells may be stacked such that the back side contact of one solar cell makes contact with the front side contact of an adjacent solar cell. In this example, the silicon solar cells may only partially overlap to provide a greater effective area of the solar panel.
Any size of the perovskite solar cell may allow for any selection of the voltage output of the perovskite top module. For example, the perovskite solar cell may be formed such that the cell generates a predetermined voltage after irradiation. The perovskite solar cell may be configured to produce a total voltage that substantially matches the silicon solar module. For example, for a silicon solar cell having a 42 volt output, the perovskite solar cell may be configured to produce 44 volts. The perovskite top module may generate a voltage that is within at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99% or greater of the voltage of the silicon solar module. The perovskite top module may produce a voltage within at most about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5% or less of the voltage of the silicon solar module. Matching of the voltage of the perovskite top module to the voltage of the silicon solar module or substation matching may create a voltage matching condition between the two modules. The voltage matching condition may produce a hybrid module having a higher current output than a voltage mismatched hybrid module. The silicon solar panel and perovskite solar panel may have substantially similar areas. For example, the perovskite layer may cover the entire silicon solar panel. In this example, the total power of the module may be maximized because all of the area of available sunlight is utilized. The perovskite solar panel may have an area of at least about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99% or more of the area of the silicon solar panel. The perovskite solar panel may have an area up to about 99%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5% or less of the area of the silicon solar panel.
Perovskite composition and additives
The perovskite layer described herein may have MA n1 FA n2 Cs n3 PbX 3 Wherein MA is methyl ammonium and FA is formamidine. n1, n2 and n3 may independently be greater than 0 and/or less than 1. n1+n2+n3 may be equal to 1. Perovskite solar cells comprising the perovskite layer may remain at least about 8 after being irradiated for 300 hours at 45 ℃ under 1sun conditions in an air atmosphereSolar energy conversion efficiency of 0%. The perovskite layer may be used as described elsewhere herein (e.g., as an absorber layer for perovskite photovoltaic cells).
In the above equation, X may be selected from 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 comprise the individual components at 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% or more. The combination may comprise the individual components at a concentration 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% or less. For example, the combination may be a mixture of about 1% chlorine and 99% iodine. The combination may comprise the individual components in concentrations within the range defined by any two of the values above. For example, the combination may be a mixture of about 1% -5% bromine and about 95% -99% iodine.
In the above formulas, n1, n2, and n3 may be individually greater than 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 greater. In the above formulas, n1, n2, and n3 may be individually less than up to about 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, 0.0001, or less. In the above formula, n1, n2, and n3 may individually have a range defined by any two of the above 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.
The cations in the formula may be as described above (e.g., methyl ammonium, formamidine, cesium, butyl ammonium). Examples of other cations that may be used include, but are not limited to, imidazolium, dimethylammonium, guanidinium, ammonium, methylamidine, tetramethylammonium, trimethylammonium, rubidium, copper, palladium, platinum, silver, gold, rhodium, ruthenium, sodium, potassium, iron, other inorganic cations, other organic cations, and the like, or any combination thereof. The perovskite layer may not contain further additives. For example, the perovskite layer may not contain thiocyanate. In another example, the perovskite layer may not include a carboxamide. The perovskite layer may be configured to provide high performance and long life without further additives. The lack of other additives may provide for lower cost and easier manufacture of the perovskite layer. Inclusion of cesium cations (or equivalent alternative cations) can increase the thermal stability of the perovskite layer. For example, the presence of cesium can increase the strength of molecular bonds of the lead halide structure of the perovskite layer. The cesium ions may also have a lower vapor pressure than the organic ions, which may contribute to the thermal stability of the perovskite layer. The inclusion of formamidine may be more tolerant of high temperatures due to the increased molecular weight compared to other organic cations (e.g., methyl ammonium). Due to the possible inherent instability of pure formamidine perovskite, the inclusion of cesium and/or methyl ammonium cations can increase crystal stability while maintaining thermal stability. The addition of too much light organic cation (e.g. methyl ammonium) reduces the thermal stability. The addition of a small percentage of butylammonium iodide may improve the quality of the perovskite layer, since the larger molecular structure of butylammonium may better fill in the gaps in the perovskite crystal structure, thereby better passivating defects or imperfections within the crystal, which in turn may enable a higher quality or performance perovskite layer.
The perovskite solar cell may be a perovskite solar cell as described elsewhere herein. 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% or more of the initial conversion efficiency value after irradiation for 300 hours under 1sun conditions at > 25 ℃ and < 100 ℃ in an air atmosphere. The perovskite layer may maintain 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% or less of the initial conversion efficiency value after irradiation for 300 hours under 1sun conditions at > 25 ℃ and < 100 ℃ in an air atmosphere. The perovskite layer may maintain a percentage of the initial conversion efficiency value defined by any two of the above values after irradiation for 300 hours under 1sun conditions at > 25 ℃ and < 100 ℃ in an air atmosphere.
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 may comprise MA n1 FA n2 Cs n3 PbX 3 Is composed of (1). MA may be methyl ammonium. The FA may be formamidine. n1, n2 and n3 may independently be greater than 0 and/or less than 1. n1+n2+n3 may be equal to 1. Perovskite solar cells comprising the perovskite layer may maintain a solar energy conversion efficiency of at least about 80% after irradiation for 300 hours under 1sun conditions at > 25 ℃ and < 100 ℃ in an air atmosphere. The perovskite layer may be subjected to an encapsulation lamination process at a temperature of at least about 120 ℃. The method may be as described elsewhere herein. For example, the method may be the process 300 of fig. 3.
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 encapsulation lamination process may be up to about 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 less. The temperature of the encapsulation lamination process may be within a temperature range defined by any two of the above values. The encapsulation may be as described elsewhere herein (e.g., with respect to encapsulant 135 of fig. 1).
The perovskite solar cell may be a perovskite solar cell as described elsewhere herein. 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% or more of the initial conversion efficiency value after irradiation for 300 hours under 1sun conditions at > 25 ℃ and < 100 ℃ in an air atmosphere. The perovskite layer may maintain 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% or less of the initial conversion efficiency value after irradiation for 300 hours under 1sun conditions at > 25 ℃ and < 100 ℃ in an air atmosphere. The perovskite layer may maintain a percentage of the initial conversion efficiency value defined by any two of the above values after irradiation for 300 hours under 1sun conditions at > 25 ℃ and < 100 ℃ in an air atmosphere. The perovskite layer may retain 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, 96, 97, 98, 99% or more of the initial conversion efficiency value after the encapsulation lamination process. The perovskite layer may maintain 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% or less of the initial conversion efficiency value after the encapsulation lamination process. The perovskite layer may maintain the efficiency of the initial conversion efficiency value after the encapsulation lamination process as defined by either of the above values.
The perovskite precursor may be applied as described elsewhere herein. For example, the perovskite precursor may be applied using an ultrasonic spray process. In this example, the precursor may be applied in a different spraying operation (e.g., lead (II) iodide may be applied to the substrate, and ammonium methyl iodide may be applied to the lead iodide). In another example, the perovskite precursor may be applied in a single operation. In this example, a solution containing all of the precursors of the perovskite layer may be applied and annealed to form the 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 ℃ or more. The annealing process may include heating the perovskite layer to a temperature of at most about 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 less. The annealing process may include heating the perovskite layer to a temperature range defined by any two of the above values.
The perovskite layer described herein may comprise MA nl FA n2 Cs n3 PbX 3 Wherein MA is methyl ammonium and FA is formamidine. n1 may have a value of about 0.01 to 0.03. n2 may have a value of about 0.82 to 0.94. n3 may have a value of about 0.05 to 0.015. n1+n2+n3 may be equal to 1.
The following examples illustrate certain systems and methods described herein and are not intended to be limiting.
Example 1 preparation of perovskite photovoltaic cells
The future frit 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 comprising a transparent conductive layer and a hole transport layer. The nickel oxide can then be laser scribed to produce a template for the individual photovoltaic cells.
Subsequently, lead (II) iodide in a solution of dimethylformamide and dimethylsulfoxide can be applied to the hole transport layer by an ultrasonic spray process. Methyl ammonium iodide in a solution of dimethylformamide and dimethyl sulfoxide can be applied to the lead (II) iodide by an ultrasonic spray process. The lead (II) iodide and methyl ammonium iodide may be annealed to allow the reaction of the two perovskite precursors and the evaporation of the solvent to form a methyl ammonium lead calcium titanium iodide ore layer. A hole transport layer of phenyl-C61-methyl butyrate (PCBM) in a solution of dimethylformamide and dimethylsulfoxide may be applied to the newly formed perovskite layer by an ultrasonic spray process. The hole transport layer may then be laser scribed along the same pattern as the nickel oxide.
Subsequently, a second transparent conductive layer of indium tin oxide may be applied by physical vapor deposition followed by a similar physical vapor deposition process to apply the silver electrode, or in another embodiment, the charge collection tape may be directly attached to the ITO layer. The electrodes may be cut by laser scribing to form an electrode assembly, and the individual photovoltaic cells may be isolated from each other by laser scribing.
The photovoltaic cells so formed can then be studied by various metrology techniques such as Scanning Electron Microscopy (SEM), optical absorption/transmission, x-ray diffraction, atomic force microscopy, ellipsometry, electroluminescence spectroscopy, photoluminescence spectroscopy, time resolved optical spectroscopy, and the like, or any combination thereof.
After the application of the second transparent conductive layer, an encapsulant can be applied to the back side of the photovoltaic cell. The encapsulant may be applied prior to isolating the photovoltaic cells by laser scribing. A first encapsulant, such as a thermoplastic polyolefin, may be applied across the back side of the photovoltaic cell, while a second encapsulant, such as butyl rubber, may be applied to the edges of the photovoltaic cell. The backside encapsulant may be optically transparent, while the side encapsulant may be optically transparent or opaque. For example, a higher quality (e.g., lower moisture and gas permeability) encapsulant may be placed on the sides of the photovoltaic cell, even though it is not optically transparent, because the sides of the cell do not absorb light, while the encapsulant for the back of the cell may be transparent to allow light to pass to the bottom junction.
Example 2 inline production of perovskite photovoltaic cells
Each operation of perovskite photovoltaic cell production may be integrated in a single instrument and/or location. For example, the substrate may be placed in a single instrument that performs all of the operations of process 300. The perovskite photovoltaic cell may be integrated with a second photovoltaic cell (e.g., a silicon photovoltaic cell) in the same instrument in which the perovskite cell was created. Fig. 10 is an example of an integrated production flow of perovskite/silicon photovoltaic cell modules. In this example, each operation may be performed in the same production line.
Large area (e.g., 1 meter x2 meters) glass substrates may be loaded onto a conveyor system configured to guide the glass substrates into the enclosure. The enclosure may include a controlled atmosphere (e.g., low humidity, oxygen content, temperature control, etc.). The enclosure may include a plurality of ultrasonic spray nozzles configured to spray a lead halide solution onto a glass substrate. After applying the lead halide solution, different nozzle groups in the enclosure may apply methyl ammonium halide and butyl ammonium halide solutions to the lead halide. The conveyor belt may be configured to move the substrate from the lead halide application nozzle to the methyl ammonium halide/butyl halide solution application nozzle within a set time period to allow formation of lead halide crystals in which the methyl ammonium halide/butyl halide may be integrated to form a perovskite layer. After application of the methyl ammonium halide and butyl ammonium halide solutions, the substrate may be moved into an annealing furnace. In another embodiment, a formulation consisting of lead halide, methyl ammonium, formamidine in a solution of dimethyl sulfoxide and methyl-2-pyrrolidone (NMP) may be applied as a single formulation by a 1-step ultrasonic spray process followed by an accelerated drying process step by application of a low vapor pressure chemical such as diethyl ether chemical and then annealed. Within the lehr, the substrate may be heated to form a perovskite layer having predetermined characteristics (e.g., grain size, thickness, elemental distribution, etc.). The lehr may be inline with the conveyor (e.g., the conveyor moves through the furnace to perform annealing). The lehr may be a batch lehr (e.g., multiple substrates may be loaded into the furnace for simultaneous annealing). The type of annealing furnace may be determined by comparing the cycle time of the furnace with the annealing duration.
After the perovskite layer is formed, the substrate may be passed through another set of ultrasonic spray nozzles for applying an electron transport layer to the perovskite layer. A second transparent conductive layer may then be applied to the electron transport layer by physical vapor deposition, an electrode may be applied by physical vapor deposition, and the individual photovoltaic cells may be isolated by laser scribing. The entire inline process may be performed on a single conveyor.
EXAMPLE 3 use of PDMS as an encapsulant
PDMS may be used as an encapsulant in a stacked 4-terminal silicon-perovskite solar module (i.e., solar module 100 of fig. 1). During lamination of the perovskite to the silicon solar cell, a PDMS encapsulant is placed between the perovskite solar cell and the silicon solar cell. Fig. 11 shows the transmission of light of various wavelengths through a perovskite solar cell without the use of PDMS encapsulant. The average percent transmission through the top TCO layer was 72.24. The average weighted transmission percentage was 74.67%. The average weighted transmission percentages are weighted according to the power delivered by the light at each wavelength. The average percent transmission through the top glass layer, top TCO layer and HTL was 72.20%. The average weighted transmission percentage was 72.68%. The average percent transmission through the perovskite solar cell was 29.20%. The average weighted transmission percentage was 24.34%. When PDMS encapsulant was used, the percent transmission to the silicon solar cell was increased to 40.44% with a weighted average of 33.48%.
Table 1 below shows the improvement in voltage and current characteristics when PDMS encapsulant is used. Specifically, the short circuit current density is from 13.93 milliamp per square centimeter ("mA/cm") when there is an air gap between the perovskite solar cell and the silicon solar cell 2 ") to 22.72mA/cm when the air gap was filled with spin-coated PDMS 2 . In table 1, "EFF" refers to efficiency. "FF" refers to the fill factor of the current/voltage plot, "aperture" refers to a test of a photovoltaic cell in which a portion of the cell is illuminated through an aperture that blocks the rest of the cell, while "cell itself" refers to a measurement of the entire cell without an aperture.
Table 1.
EXAMPLE 4 use of PDMS on top glass plate
PDMS may be applied to the top glass plate of a laminated 4-terminal silicon-perovskite solar module (i.e., solar module 100 of fig. 1). Table 2 shows the rise in short circuit current density obtained when these different types of PDMS were used. The improvement is a result of better light trapping and index matching as light propagates from air through PDMS to glass to the perovskite solar cell.
TABLE 2
Example 5 Performance of solar modules with and without ultra thin silver layers
As mentioned in this disclosure, PVD of the second TCO layer over the ETL may create defects in both the perovskite layer and the ETL of the stacked 4-terminal silicon-perovskite solar module (i.e., solar module 100 of fig. 1). By including an ultra-thin silver layer deposited at the interface between the ETL and the second TCO layer, the defects can be minimized.
As shown in fig. 15, the current and voltage (IV) performance of the solar module with the ultra-thin silver layer is superior to the solar module without the ultra-thin silver layer. The ultra-thin silver layer yields better performance due to the increased barrier and shielding effect of silver during the tcovd process. Without a silver layer, the solar module has a reduced Fill Factor (FF) due to an increase in the number of defect sites at the interface between the second TCO layer and the ETL and/or in the bulk of the ETL and perovskite layers caused by the tcovd process.
Table 3 further illustrates the improved performance of solar modules comprising a superb layer. For example, with a silver layer, the solar module shows 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).
TABLE 3 Table 3
Example 6 Performance of solar modules fabricated in an inline PVD Process
As described herein, a 4-terminal silicon-perovskite solar module (i.e., solar module 100 of fig. 1) may be fabricated in an inline manufacturing process. The inline fabrication process reduces the amount of ion damage and UV exposure of the ETL and perovskite layers during PVD, resulting in improved efficiency of the resulting solar module.
Table 4 illustrates the efficiency improvement of solar modules manufactured in an inline manufacturing process. Table 4 (in bold text) indicates the specifics of solar modules exhibiting high efficiency, fill factor and open circuit voltage due to the inline manufacturing process. Table 4 also illustrates that the inline manufacturing process is sufficiently effective in reducing defects in the ETL and perovskite layers that the addition of an ultra-thin silver layer is not necessarily required. As shown in table 4, the ultra-thin silver layer does not provide the same efficiency improvement as solar modules fabricated without the inline fabrication process (e.g., comparing the data in table 4 with the data provided in table 3 of example 5).
Example 7-Electrical connection of stacked solar modules
Fig. 16-19 show examples of different electrical network connections for different types of silicon-perovskite hybrid solar modules. The detail illustrations may illustrate electrical connections of the silicon-perovskite hybrid solar module. Leads from the perovskite solar module may be connected to leads of the silicon solar module. For example, a perovskite solar module may comprise a plurality of perovskite strip solar cells connected in series. Silicon solar cells may be connected in a similar manner. This can result in two leads from the silicon solar module and two leads from the perovskite solar module. These leads can then be connected together and to a junction box for transmitting electrical energy out of the solar module. This approach of connecting a silicon solar module and a perovskite solar module to form a hybrid solar module may be applicable to any geometry of silicon and perovskite solar cells. For example, the silicon module may include a front contact silicon solar cell, an integrated back contact silicon solar cell, a roof silicon solar cell, and the like. In another example, the perovskite solar cell may be a ribbon solar cell, a tiled solar cell, a front contact solar cell, or the like. The perovskite solar cell may comprise a plurality of cells comprising a plurality of perovskite strip solar cells connected in series. For example, a plurality of cells each comprising a plurality of perovskite strip solar cells may be connected in parallel in a voltage matching scheme.
In one example of a hybrid module, 6 by 10 arrays of silicon solar cells are electrically connected in series to form a silicon solar module with an open circuit voltage of 0.7vx60=42V. The perovskite layer was cut by laser scribing to form 40 ribbon solar cells. Each strip is about 20mm wide by 300mm long. The 40 strips are connected in series. The strips may be connected, for example, by a P1/P2/P3 layer method. The connected strips may in turn be connected to each other by an electrode/charge collection strip placed at the end of the connected strips as described elsewhere herein. Each strip may have an open circuit voltage of 1.1V, and the 40 series-connected strips may have a total voltage of 1.1V x 40 = 44V. To achieve full coverage of the silicon solar panel, five units of 40 ribbon solar cells may be tiled on the same glass plate. The cells may in turn be connected in parallel to maintain a voltage matching condition. This may result in a substantially voltage matched hybrid module.
Example 8 Performance of Mixed composition perovskite solar cell
As described elsewhere herein, a perovskite layer (e.g., 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 laminated solar module. Furthermore, the mixed composition may be used to tailor the properties of the perovskite layer to suit a particular application.
Fig. 21 is a graph illustrating the efficiency of three perovskite solar cells during reliability testing at extended 85 ℃ and 85% relative humidity (85 ℃/85%). Such a reliability test may be an accelerated aging test, which may show long-term stability of the solar cell against moisture or atmospheric ingress. As seen in fig. 21, the solar cell may show little degradation even during a long test time. This slow degradation may be caused by a combination of the composition of the perovskite layer and the encapsulation quality of the perovskite layer. The modules may have performance required by standardized tests. For example, such a module may pass reliability tests such as the IEC 61215 or IEC61646 standards and even exceed the performance of the standards (e.g. still pass the standards after 4000 hours of testing).
Fig. 22A-22B show examples of efficiency degradation of perovskite solar cells under dark thermal stress testing (fig. 22A) and under 1-sun irradiation at maximum power point thermal stress testing (fig. 22B). Perovskite solar cells comprising formamidine may show little to no degradation at 65 ℃ and no irradiation, confirming that the heavier cations impart improved thermal stability compared to the slight thermal degradation of solar cells comprising methylammonium. The performance improvement of formamidine-containing solar cells can become more pronounced at 65 ℃ and under irradiation, and the performance loss of formamidine solar cells is less than one-fourth of that of methylammonium solar cells.
FIGS. 23A-23C are high temperature aging diagrams showing a composition MA 0.2 FA 0.88 Cs 0.1 PbI 3 Open and short circuit of perovskite solar cell at various different temperaturesAnd a maximum power point efficiency map. As seen in fig. 23B, under the same conditions, the mixed composition perovskite performed better than the corresponding methyl ammonium only or formamidine only perovskite from fig. 17B.
Table 5 illustrates the composition Cs 0.12 FA 0.88 MA 0.02 PbCl 0.01 Br 0.09 I 0.9 Is a thermally stable perovskite. The perovskite solar cell was still able to maintain a high solar conversion efficiency of 18.64% despite being subjected to a relatively high temperature annealing operation. Such high efficiency demonstrates the high stability that can be achieved in mixed composition perovskites.
TABLE 5
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Table 6 illustrates various parameters of perovskite solar cells with different types of edge seals prior to high temperature (e.g., > 120 ℃) encapsulation lamination process, immediately after lamination, after 10 minutes of annealing operation at 100 ℃ and after two days. The first column provides data for perovskite solar cells without edge seals, while the middle column is two edge sealed perovskite solar cells and the right column is all four edge sealed perovskite solar cells. In each case, the perovskite solar cell is able to recover most, if not all, of its original efficiency after annealing. Such thermal stability may allow for the use of higher quality and higher temperature encapsulation processes, which in turn may increase the lifetime and efficiency of the solar cell.
TABLE 6
Example 9 scalable fabrication method of perovskite solar cell
Spray precursor solutions comprising lead (II) halide, methyl ammonium iodide, cesium, formamidine, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone can be formed as described elsewhere herein. For example, the precursors or salts thereof may be mixed together, stirred and heated slightly to improve uniformity. The resulting precursor solution may be applied to the substrate by an ultrasonic spray process and dried at room temperature for 5-15 minutes. The substrate with the precursor layer may then be immersed in an anti-solvent to form the perovskite layer. Examples of immersing include immersing the substrate in an anti-solvent, mechanical spraying of the anti-solvent, chemical spraying of the anti-solvent, and the like, or any combination thereof. Slow addition of the perovskite film to the antisolvent can effectively reduce defects in the film and residues left on the film. For example, the back and forth movement of the membrane during addition to the anti-solvent bath can create defects in the contact line between the membrane and the anti-solvent. The substrate may be slowly introduced into the solvent bath to avoid such defects. Alternatively, controlled irrigation followed by drying with an air knife can produce high quality perovskite films.
Examples of antisolvents include, but are not limited to, diethyl ether, dibutyl ether, chlorobenzene, chloroform, and the like, or any combination thereof. The choice of anti-solvent may depend on the miscibility of the anti-solvent with the solvent (e.g., the solvent and anti-solvent may be miscible), the solubility of the perovskite in the anti-solvent (e.g., the anti-solvent may not be effective in dissolving the perovskite), etc. Rapid removal of the solvent by means of an antisolvent may be important to the overall quality of the film. For example, if the anti-solvent does not completely remove the solvent, an impenetrable skin may form on top of the layer and inhibit further removal of the solvent. In another example, rapid removal of solvent may result in a high quality film. The soaked effluent may be recovered, regenerated (e.g., by removal of solid particles), and reused to produce the next perovskite layer. The perovskite layer may then be annealed as described elsewhere herein. For example, the perovskite layer may be annealed at a temperature between 90 ℃ and 110 ℃ for 5-15 minutes and then at 110 ℃ for 10 minutes. Fig. 24A is an example of an apparatus for producing a perovskite layer including using an antisolvent according to one embodiment.
This method of producing perovskite films can produce perovskite solar cells with good performance and low hysteresis. Table 7 shows an example of the properties of perovskite films of about 350nm thickness prepared by this method. FIG. 25 illustrates an exemplary histogram of the efficiency of various perovskite layers produced by the methods and systems described herein according to one embodiment. This figure demonstrates the feasibility of producing a consistent high performance perovskite solar module for use in the devices described herein. Other parameter adjustments as described elsewhere herein may also result in further improvements in the efficiency and consistency of perovskite module products.
TABLE 7
An antisolvent-free method of preparing a perovskite layer may include using a precursor solution including lead (II) acetate, lead (II) halide, methyl ammonium halide, and dimethylformamide. This solution may not utilize the application of an anti-solvent to form the perovskite layer. For example, the solution may be applied to a substrate and allowed to dry at room temperature for 5-15 minutes to form a perovskite layer. The perovskite layer may then be annealed as described elsewhere herein. Fig. 24B is an example of an apparatus for producing a perovskite layer without using an anti-solvent according to one embodiment.
Such methods may be scalable due to a combination of simple atmosphere control (e.g., low humidity ambient conditions), one-shot perovskite spray formulation, scalable drying process (e.g., vacuum, air knife, etc.), scalable annealing process, and scalable electron transport layer addition (e.g., ultrasonic spray formulation and equipment).
Example 10 reliability test and packaging
FIG. 26 is a schematic diagram of an exemplary solar module package according to one embodiment. Fig. 27 is a schematic diagram of an exemplary wiring diagram of a module package according to one embodiment. The exemplary solar module package may be a hybrid module comprising a perovskite layer 2601 and a silicon layer 2602. The perovskite layer may be formed by the methods and systems described elsewhere herein. For example, the perovskite layer may be formed on a top glass sheet of a silicon solar module. The perovskite layer may be placed on top of a hole transport layer which itself is placed on top of a transparent conductive oxide layer of about 7 ohms/square as described elsewhere herein. An electron transport layer may then be added to the perovskite layer, and another transparent conductive oxide layer may be added over the electron transport layer. A metal layer may then be added to form an electrode contact configured to remove current from the perovskite layer. The perovskite on glass may then be overlaid on a series connected 2x2 array of 6 inch silicon solar cells. As shown, the perovskite solar cell may be connected in parallel with a silicon solar cell. Alternatively, the perovskite and silicon solar cell may be electronically separated (e.g., a 4-terminal architecture). The perovskite layer may be placed in a glass-to-glass configuration with a silicon solar cell. The glass-to-glass configuration may improve light trapping within the solar module and thus improve the overall efficiency of the module. As shown in fig. 27, the perovskite layer may be laser scribed into multiple strips so that the open circuit voltage of the perovskite battery may be matched to the open circuit voltage of the silicon cell. Such voltage matching may reduce waste and improve overall performance of the module.
The modules may be tested to ensure that the performance of the modules remains unchanged over time. Such tests may include performance tests (e.g., performance measurements, temperature coefficient measurements, normal operation battery temperature measurements, low light irradiation performance, light-induced degradation measurements, light and high temperature-induced degradation measurements, etc.), environmental durability tests (e.g., temperature cycling, humidity freeze tests, damp heat tests, potential-induced degradation tests, etc.), long-term durability tests (e.g., outdoor exposure tests, hot spot tests, reverse current overload tests, UV modulation, hail durability, etc.), etc., or any combination thereof.
Computer system
The present disclosure provides a computer system programmed to perform the methods of the present disclosure. Fig. 12 illustrates a computer system 1201 that is programmed or otherwise configured to direct the manufacturing and fabrication processes described herein (e.g., physical vapor deposition, ultrasonic spray coating, etc.) or to control power electronics connected to the solar modules described herein.
The computer system 1201 includes a central processing unit (CPU, also referred to herein as a "processor" or "computer processor") 1205, which may be a single or multi-core processor, or multiple processors for parallel processing. The computer system 1201 also includes a memory or storage location 1210 (e.g., random access memory, read only memory, flash memory), an electronic storage unit 1215 (e.g., a hard disk), a communication interface 1220 (e.g., a network adapter) for communicating with one or more other systems, and peripheral devices 1225 such as cache, other memory, data storage, and/or electronic display adapters. The memory 1210, the storage unit 1215, the interface 1220, and the peripheral device 1225 communicate with the CPU 1205 through a communication bus (solid line) such as a motherboard. The storage unit 1215 may be a data storage unit (or data repository) for storing data. The computer system 1201 may be operatively coupled to a computer network ("network") 1230 with the aid of a communication interface 1220. The network 1230 may be the internet, and/or an extranet, or an intranet and/or an extranet in communication with the internet. In some cases, network 1230 is a telecommunications and/or data network. Network 1230 may include one or more computer servers, which may implement distributed computing such as cloud computing. In some cases, with the aid of the computer system 1201, the network 1230 may implement a peer-to-peer network that enables devices coupled to the computer system 1201 to act as clients or servers.
The CPU 1205 may execute a series of machine readable instructions that may be embodied in a program or software. The instructions may be stored in a memory location, such as memory 1210. The instructions may be directed to the CPU 1205, which may then program or otherwise configure the CPU 1205 to implement the methods of the present disclosure. Examples of operations performed by the CPU 1205 may include fetch, decode, execute, and write back.
The CPU 1205 may be part of a circuit such as an integrated circuit. One or more other components of system 1201 may be included in the circuit. In some cases, the circuit is an Application Specific Integrated Circuit (ASIC).
The storage unit 1215 may store files such as drivers, libraries, and saved programs. The storage unit 1215 may store user data such as user preferences and user programs. In some cases, the computer system 1201 may include one or more additional data storage units external to the computer system 1201, such as on a remote server in communication with the computer system 1201 via an intranet or the Internet.
The computer system 1201 may communicate with one or more remote computer systems over a network 1230. For example, the computer system 1201 may communicate with a user's remote computer system. Examples of remote computer systems include personal computers (e.g., portable PCs), tablet or slate PCs (e.g. Tab), phone, smart phone (e.g +.>Android-enabled device->) Or a personal digital assistant. A user may access the computer system 1201 via the network 1230.
The methods described herein may be implemented by machine (e.g., a computer processor) executable code stored on an electronic storage location of the computer system 1201, such as the memory 1210 or the electronic storage unit 1215. The machine-executable code or machine-readable code may be provided in the form of software. During 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 on the memory 1210 for ready access by the processor 1205. In some cases, the electronic storage unit 1215 may be eliminated and the machine executable instructions stored on the memory 1210.
The code may be pre-compiled and configured for use with a machine having a processor adapted to execute the code, or may be compiled at runtime. The code may be provided in a programming language, which may be selected to enable the code to be executed in a pre-compiled or compiled manner.
Various aspects of the systems and methods provided herein, such as the computer system 1201, may be embodied in programming. Aspects of the technology may be considered to be "articles of manufacture" or "articles of manufacture" and are typically loaded onto or embodied in some type of machine-readable medium in the form of machine (or processor) executable code and/or associated data. The machine executable code may be stored on an electronic storage unit such as a memory (e.g., read only memory, random access memory, flash memory) or a hard disk. A "storage" type of medium may include any or all of the tangible memory of a computer, processor, etc., or related modules thereof, such as various semiconductor memories, tape drives, disk drives, etc., which may provide non-transitory storage for software programming at any time. All or a portion of the software may sometimes communicate over the internet or various other telecommunications networks. For example, such communication may enable loading of software from one computer or processor into another, such as from a management server or host computer into a computer platform of an application server. Thus, another type of medium that can carry software elements includes optical, electrical, and electromagnetic waves, such as those used through physical interfaces between local devices, through wired and optical landline networks, and through various air links. Physical elements carrying such waves, such as wired or wireless links, optical links, etc., may also be considered as media carrying software. As used herein, a term such as a computer or machine "readable medium" refers to any medium that participates in providing instructions to a processor for execution, unless limited to non-transitory, tangible "storage" media.
Thus, a machine-readable medium, such as a computer-executable code, may take many forms, including but not limited to, tangible storage media, carrier wave media, or physical transmission media. Nonvolatile storage media includes, for example, optical or magnetic disks, any storage devices, such as any computers, etc., such as may be used to implement the databases shown in the figures. Volatile storage media include dynamic memory, such as the main memory of such a computer platform. Tangible transmission media include coaxial cables, copper wire and fiber optics, including the wires that comprise a bus within a computer system. Carrier wave transmission media can 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 communications. Thus, common forms of computer-readable media include, for example, a floppy disk, a flexible disk, hard disk, magnetic tape, any other magnetic medium, a CD-ROM, DVD, or DVD-ROM, any other optical medium, punch cards paper tape, any other physical storage medium with patterns of holes, RAM, ROM, PROM and EPROM, a FLASH-EPROM, any other memory chip or cartridge, a carrier wave transporting data or instructions, a cable or link transporting such a carrier wave, or any other medium from which a computer can read programming code and/or data. Many of these forms of computer readable media may be involved in carrying one or more sequences of one or more instructions to a processor for execution.
The computer system 1201 may include or be in communication with an electronic display 1235, the display 1235 containing a User Interface (UI) 1240 for providing, for example, control of manufacturing process parameters. Examples of UIs include, but are not limited to, graphical User Interfaces (GUIs) and web-based user interfaces.
The methods and systems of the present disclosure may be implemented by one or more algorithms. The algorithm may be implemented in software after execution by the central processing unit 1205.
Although preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. The present invention is not intended to be limited by the specific examples provided in this specification. Although the invention has been described with reference to the foregoing specification, the description and illustrations of the embodiments herein are not meant to be construed in a limiting sense. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. Furthermore, it is to be understood that all aspects of the invention are not limited to the specific descriptions, configurations, or relative proportions set forth herein, as such may be dependent upon a variety of different conditions and variables. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is therefore contemplated that the present invention shall also cover any such alternatives, modifications, variations or equivalents. The claims are intended to define the scope of the invention and the method and structure within the scope of these claims and their equivalents are covered thereby.

Claims (55)

1. A method, comprising:
(a) Providing a silicon solar module having a first voltage output, wherein the silicon solar module comprises a top glass panel;
(b) Forming a perovskite layer on the top glass panel;
(c) Fabricating one or more perovskite solar cells from the perovskite layer, wherein the one or more perovskite solar cells produce a voltage that substantially matches the voltage output of the silicon solar module; and
(d) The silicon solar module is electrically connected to the one or more perovskite solar cells.
2. The method of claim 1, wherein the fabricating comprises defining the one or more perovskite solar cells using laser scribing.
3. The method of claim 1, wherein the one or more perovskite solar cells are a plurality of perovskite solar cells.
4. A method according to claim 3, wherein the plurality of perovskite solar cells are connected in series.
5. The method of claim 1, further comprising applying a plurality of contacts to the one or more perovskite solar cells to electrically couple the one or more perovskite solar cells.
6. The method of claim 1, further comprising applying an encapsulant to the one or more perovskite solar cells.
7. The method of claim 6, wherein the encapsulant is a thermoplastic polyolefin.
8. The method of claim 7, wherein the encapsulant is ethylene vinyl acetate.
9. The method of claim 1, further comprising applying an edge seal to the one or more perovskite solar cells.
10. A stacked solar module, comprising:
a silicon solar panel comprising (i) a plurality of silicon solar cells connected in series and (ii) a top glass plate, wherein the plurality of silicon solar cells are connected in series and together have a first open circuit voltage;
a perovskite solar panel configured on a bottom surface of the top glass sheet of the silicon solar panel, wherein the perovskite solar panel comprises a plurality of sections, wherein each section of the plurality of sections comprises a plurality of laser-scribed perovskite strips, wherein the plurality of laser-scribed perovskite strips within a section are connected in series to produce a second open circuit voltage that is substantially the same as the first open circuit voltage; and
An interconnect connects the plurality of silicon solar cells in parallel with the plurality of sections of the perovskite solar panel.
11. The module of claim 10, wherein the plurality of segments comprises from about 10 to about 200 segments.
12. The module of claim 10, wherein the silicon solar panel is a top contact solar panel, an integrated back contact solar panel, or a roof solar panel.
13. The module of claim 10, wherein the silicon solar panel and the perovskite solar panel are connected to the same junction box.
14. The module of claim 10, wherein the silicon solar panel and the perovskite solar panel have substantially similar areas.
15. The module of claim 10, wherein the plurality of laser scribed perovskite strips are connected by a P1/P2/P3 scheme.
16. A perovskite layer, comprising:
MA n1 FA n2 Cs n3 PbX 3 wherein MA is methyl ammonium, FA is formamidine, n1, n2, and n3 are independently greater than 0 and less than 1, and n1+n2+n3=1, wherein a perovskite solar cell comprising the perovskite layer maintains at least about 80% solar conversion efficiency after 300 hours of irradiation in an air atmosphere at > 25 ℃ and < 100 ℃ under 1sun conditions.
17. The perovskite layer of claim 16, wherein X is selected from fluorine, chlorine, bromine, and iodine.
18. The perovskite layer of claim 17, wherein X is a combination of two or more of fluorine, chlorine, bromine, and iodine.
19. The perovskite layer of claim 16, wherein n1 is about 0.001 to about 0.05.
20. The perovskite layer of claim 16, wherein n3 is about 0.001 to about 0.15.
21. The perovskite layer of claim 16, wherein the solar conversion efficiency is at least about 90% of an initial conversion efficiency value after irradiation for 300 hours under 1sun conditions.
22. The perovskite layer of claim 21, wherein the solar conversion efficiency is at least about 95% of an initial conversion efficiency value after irradiation for 300 hours under 1sun conditions.
23. The perovskite layer of claim 16, wherein the perovskite layer does not contain other additives.
24. A method, comprising:
(a) Providing a substrate;
(b) Applying a perovskite precursor to the substrate;
(c) Annealing the perovskite precursor to form a perovskite layer; wherein the perovskite layer has MA nl FA n2 Cs n3 PbX 3 Wherein n1, n2, and n3 are independently greater than 0 and less than 1, and n1+n2+n3=1, wherein a perovskite solar cell comprising the perovskite layer maintains at least about 80% solar conversion efficiency after 300 hours of irradiation at 1sun condition at > 25 ℃ and < 100 ℃; and
(d) The perovskite layer is subjected to an encapsulation lamination process at a temperature of at least about 120 ℃.
25. The method of claim 24, wherein the perovskite solar cell retains at least about 80% of an initial conversion efficiency value after the encapsulation lamination process.
26. The method of claim 25, wherein the perovskite solar cell retains at least about 97% of an initial conversion efficiency value after the encapsulation lamination process.
27. The method of claim 24, wherein applying the perovskite precursor is performed by an ultrasonic spray process.
28. The method of claim 24, wherein the annealing process comprises heating the perovskite layer to a temperature of at least about 40-120 ℃.
29. A perovskite layer, comprising:
MA n1 FA n2 Cs n3 PbX 3 wherein MA is methyl ammonium, FA is formamidine, 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.
30. The perovskite layer of claim 29, wherein X is selected from fluorine, chlorine, bromine, and iodine.
31. The perovskite layer of claim 30, wherein X is a combination of two or more of fluorine, chlorine, bromine, and iodine.
32. The perovskite layer of claim 29, wherein the perovskite solar cell does not contain other additives.
33. A device, comprising:
a silicon solar cell having a first bandgap;
a top glass sheet covering the silicon solar cell, wherein the top glass sheet comprises a top surface and a bottom surface; and
a perovskite solar cell having a second bandgap, wherein the perovskite solar cell is deposited on a bottom surface of the top glass sheet.
34. The device of claim 33, wherein the silicon solar cell is electrically insulated from the perovskite solar cell.
35. The device of claim 34, wherein the silicon solar cell comprises two terminals and the perovskite solar cell comprises two terminals.
36. The device of claim 33, wherein the perovskite solar cell comprises a photoactive perovskite layer, wherein the photoactive perovskite layer comprises CH 3 NH 3 PbX 3 Or H 2 NCHNH 2 PbX 3 。
37. The device of claim 36, wherein X comprises iodine, bromine, chloride ions, or a combination thereof.
38. The device of claim 33, wherein the perovskite solar cell comprises a first Transparent Conductive Oxide (TCO) layer and a second TCO layer.
39. The device of claim 38, wherein the first and second TCO layers are terminals of the perovskite solar cell.
40. The device of claim 39, wherein the first and second TCO layers comprise indium oxide, indium tin oxide, or aluminum zinc oxide.
41. The device of claim 33, wherein the perovskite solar cell comprises an Electron Transport Layer (ETL) comprising phenyl-C61-butyrate methyl ester or C60.
42. The device of claim 33, wherein the perovskite solar cell comprises a Hole Transport Layer (HTL) comprising nickel oxide.
43. The device of claim 33, further comprising a plurality of silicon solar cells including the silicon solar cell and a plurality of perovskite solar cells including the perovskite solar cell, wherein the plurality of perovskite solar cells are laser scribed in the top glass sheet to voltage match or current match the plurality of perovskite solar cells with the plurality of silicon solar cells.
44. The device of claim 33, wherein the top glass sheet has a surface area substantially corresponding to a surface area of a 60 or 72 cell solar panel.
45. The device of claim 33, wherein a top surface of the top glass sheet comprises an anti-reflective coating.
46. The device of claim 33, wherein a top surface of the top glass plate comprises Polydimethylsiloxane (PDMS).
47. The apparatus of claim 46, wherein the PDMS comprises 1:10 alumina PDMS, textured 1:50 alumina PDMS or textured PDMS.
48. The apparatus of claim 33, wherein a bottom surface of the top glass plate has a textured surface.
49. The device of claim 33, further comprising an encapsulant disposed between the silicon solar cell and perovskite solar cell.
50. The device of claim 33, wherein the encapsulant is selected from the group consisting of ethylene vinyl acetate ("EVA"), thermoplastic polyolefin ("TPO"), PDMS, silicone, and paraffin.
51. The device of claim 33, wherein the silicon solar cell and perovskite solar cell are electrically connected in parallel.
52. The device of claim 33, wherein the silicon solar cell and perovskite solar cell are electrically connected in series.
53. The device of claim 33, wherein the second bandgap is between about 1.5 and 1.9 electron volts (eV).
54. The device of claim 33, wherein the silicon solar cell is selected from the group consisting of single crystal solar cells, polycrystalline solar cells, passivated emitter back contact (PERC) solar cells, interdigitated back contact cells (IBC), and heterojunction with intrinsic thin layer (HIT) solar cells.
55. A method of manufacturing a solar module, the method comprising:
(a) Providing a silicon solar cell having a first bandgap;
(b) Forming a perovskite solar cell having a second band gap in a bottom surface of the glass sheet; and
(c) The glass sheet is adhered to a silicon solar cell to form the solar module such that a bottom surface of the glass sheet is adjacent to the silicon solar cell.
CN202180064458.1A 2020-09-22 2021-09-22 Method and apparatus for integrated stacked solar module fabrication Pending CN116547104A (en)

Applications Claiming Priority (19)

Application Number Priority Date Filing Date Title
US63/081,758 2020-09-22
US63/081,753 2020-09-22
US63/081,750 2020-09-22
US63/081,747 2020-09-22
US63/081,752 2020-09-22
US63/081,756 2020-09-22
US63/081,755 2020-09-22
US63/090,642 2020-10-12
US63/090,643 2020-10-12
US63/090,636 2020-10-12
US16/953,247 2020-11-19
US63/126,481 2020-12-16
US63/126,483 2020-12-16
US63/159,277 2021-03-10
US63/176,845 2021-04-19
US202163196585P 2021-06-03 2021-06-03
US63/196,585 2021-06-03
US63/196,601 2021-06-03
PCT/US2021/051465 WO2022066707A1 (en) 2020-09-22 2021-09-22 Methods and devices for integrated tandem solar module fabrication

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