WO2020243287A1 - Procédé de fabrication d'une couche de pérovskite à grande vitesse - Google Patents

Procédé de fabrication d'une couche de pérovskite à grande vitesse Download PDF

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WO2020243287A1
WO2020243287A1 PCT/US2020/034901 US2020034901W WO2020243287A1 WO 2020243287 A1 WO2020243287 A1 WO 2020243287A1 US 2020034901 W US2020034901 W US 2020034901W WO 2020243287 A1 WO2020243287 A1 WO 2020243287A1
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Prior art keywords
perovskite
percent
perovskite solution
solution
layer
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PCT/US2020/034901
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English (en)
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Scott Kenneth CHRISTENSEN
Qi Li
Thomas Nathaniel Tombs
Stephan J. Deluca
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Energy Materials Corporation
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Priority claimed from US16/426,341 external-priority patent/US11342130B2/en
Priority claimed from US16/426,191 external-priority patent/US11108007B2/en
Priority claimed from US16/426,439 external-priority patent/US20200377532A1/en
Application filed by Energy Materials Corporation filed Critical Energy Materials Corporation
Priority to MX2021014434A priority Critical patent/MX2021014434A/es
Priority to EP20814928.6A priority patent/EP3977529A4/fr
Priority to US17/615,142 priority patent/US20220238807A1/en
Priority to CN202080052785.0A priority patent/CN114514624A/zh
Priority to CA3142260A priority patent/CA3142260A1/fr
Priority to KR1020217043326A priority patent/KR20220054249A/ko
Priority to JP2021570823A priority patent/JP7519701B2/ja
Publication of WO2020243287A1 publication Critical patent/WO2020243287A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/24—Lead compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to depositing a perovskite solution at high speed on a flexible substrate, drying the solution and, more particularly, a novel method of making perovskite layers and perovskite photovoltaic devices.
  • the present disclosure further relates to methods of making a photovoltaic device on a substrate at high speed with a Perovskite solution.
  • the present disclosure further relates to the composition of a Perovskite solution for use in making Perovskite layer and Perovskite photovoltaic devices at high speed.
  • PSCs halide perovskite solar cells
  • PSCs advantages and high PCE put them on the path to be the next generation technology for utility, commercial, and residential photovoltaic applications.
  • Most top performing PSCs have been fabricated by a spin-coating method, which is unsuitable for high throughput and scalable module production.
  • several scalable film deposition techniques have been developed for PSC fabrication, such as doctor-blading, spray deposition, slot-die coating, gravure coating, inkjet printing, dip coating, chemical bath deposition, flexographic, and electrodeposition.
  • a next step towards the scalable fabrication of PSCs is to develop methods to make the perovskite layer using high speed equipment suitable for high volume manufacturing.
  • the speed of production In order for PSCs to gain market share in existing solar markets the speed of production must be fast enough so that the capital equipment costs do not overly burden the ability to scale up for production and also so that the final cost of PSCs is competitive with the already mature manufacturing state of silicon-based solar cells. While the methods cited above are scalable in principle, they have not yet demonstrated deposition speeds necessary to produce low-cost PSCs that can compete with the current silicon technologies. Forming uniform and defect free perovskite layers on flexible multilayer substrates to make PSCs in a cost-effective manner remains a great challenge due to the complexity of depositing and drying a perovskite solution with high speed production equipment.
  • a method of making a perovskite layer comprising: providing a flexible substrate; providing a perovskite solution comprising an initial amount of solvent and perovskite precursor materials and having a provided solution temperature and a total solids concentration between 30 percent and 70 percent by weight of its saturation concentration at the provided solution temperature; depositing the perovskite solution on the flexible substrate at a first location; removing a first portion of the initial amount of solvent from the deposited perovskite solution with a first drying step having a first drying step dwell time at a second location wherein the first drying step heats the deposited perovskite solution to a coated layer temperature and increases the total solids concentration of the perovskite solution to at least 75 percent of its saturation concentration at the coated layer temperature; and removing a second portion of the initial amount of solvent from the deposited perovskite solution with a second drying step having a higher rate of solvent evaporation than the first drying step during a second drying step
  • a method of making a photovoltaic device comprising: providing a substrate; depositing a first carrier transport solution layer with a first carrier transport deposition device to form a first carrier transport layer on the substrate; depositing a Perovskite solution comprising solvent and perovskite precursor materials with a perovskite solution deposition device on the first carrier transport layer; drying the deposited Perovskite solution to form a Perovskite absorber layer; and depositing a second carrier transport solution with a second carrier transport deposition device to form a second carrier transport layer on the Perovskite absorber layer, wherein the deposited Perovskite solution is dried at least partially with a fast drying device which causes a conversion reaction and the Perovskite solution to change in optical density by at least a factor of 2 in less than 0.5 seconds after the fast drying device first acts on the Perovskite solution.
  • a Perovskite solution for making a Perovskite layer comprises a solvent, an organic Perovskite precursor material, and an inorganic Perovskite precursor material, wherein the amount of solvent is greater than 30 percent by weight and the Perovskite solution has a total solids concentration that is between 30 percent and 70 percent by weight of the Perovskite solution’s saturation concentration at a solution temperature of from 20 to 25 degrees Celsius.
  • Various embodiments in accordance with the disclosure have the advantage that a uniform perovskite layer can be manufactured at high speed on a flexible substrate, and in particular embodiments a flexible multilayer substrate, thereby enabling, e.g., low cost production of high efficiency solar cells with low equipment costs.
  • Various further embodiments in accordance with the disclosure have the advantage that a Perovskite photovoltaic device can be manufactured at high speed, thereby enabling, e.g., low cost production of a new class of photonic devices such as high efficiency solar cells.
  • FIG. 1 illustrates a cross section of a portion of a perovskite device wherein multiple functional layers are shown on a flexible support;
  • FIGS. 2a, 2b, 2c, and 2d illustrate in cross sections the formation of the perovskite layer on a portion of a multilayer flexible substrate after important steps in various embodiments of the disclosure.
  • FIG. 2a shows the perovskite solution on a flexible multilayer substrate after the deposition of the perovskite solution.
  • FIG. 2b shows a partially dry perovskite layer solution after the first drying step.
  • FIG. 2c shows an immobile layer of perovskite crystals or intermediate phase on a flexible multilayer substrate after a second drying step.
  • FIG. 2d shows the completed perovskite layer on the flexible multilayer substrate after an annealing step;
  • FIG. 3 is a schematic side view of an exemplary printing system for roll- to-roll printing on a flexible multilayer substrate.
  • FIG. 4 is a schematic side view of an exemplary multi-station deposition and drying device for roll-to-roll printing a photovoltaic device on a flexible multilayer substrate.
  • FIG. 1 Shown in FIG. 1 is a cross section of a portion of a perovskite device, 67.
  • the structure of the perovskite device 67 comprises a relatively thick (e.g., 5 to 200 microns) flexible support 61 with several, much thinner, functional layers.
  • first conducting layer 62 On top of the flexible support 61 is first conducting layer 62, a first carrier transport layer 63, a completed perovskite layer 64d, a second carrier transport layer 65, and a second conducting layer 66.
  • Support 61, along with layers 62 and 63 form a multilayer substrate 60 for perovskite layer 64, as further shown in Figs. 2a-2d.
  • the first conducting layer 62 and the first carrier transport layer 63 are optically transparent in the frequency range that the perovskite layer 64d converts photons into electron-hole pairs, typically the visible frequency range.
  • the second conducting layer 66 and the second carrier transport layer 65 are optically transparent in the frequency range that the perovskite layer 64d converts photons into electron-hole pairs.
  • the optically transparent carrier transport layer transports holes and blocks electrons.
  • the optically transparent carrier transport layer transports electrons and blocks holes.
  • perovskite solution is defined as a solution or colloidal suspension that can be used to generate a continuous layer of organic-inorganic hybrid perovskite material (referred here as perovskite layer) with an ABX3 crystal lahice where ⁇ ' and 'B' are two cations of very different sizes, and X is an anion that coordinates to both cations.
  • a perovskite solution comprises perovskite precursor material and solvent, and may also contain additives to aid in crystal growth or to modify crystal properties.
  • Perovskite precursor material is defined as an ionic species where at least one of its constituents becomes incorporated into the final perovskite layer ABX3 crystal lahice.
  • Organic perovskite precursor material are materials whose cation contains carbon atoms while inorganic perovskite precursor material are materials whose cation contains metal but does not contain carbon.
  • perovskite solution For small quantities of perovskite solution, a high concentration of precursor materials can be used when making high performance lab-scale coatings. However, when depositing perovskite solution at high speed on pilot scale or full- scale manufacturing equipment these high concentration solutions have been found to be unstable for the required duration to enable a uniform coating. Unstable solutions form non-colloidal solids in the solution prior to coating that inhibit the deposition and drying process and produce nonfunctional photovoltaic devices. Hence, lower concentrations of precursors must be specified for high speed coatings. Lower concentration solutions require thicker wet coatings to achieve the appropriate dry thickness for the perovskite layer. For thicker wet coatings it has been found that simple drying methods do not produce a uniform coating suitable for functional photovoltaic devices.
  • a second reason for the variability in the dry perovskite layer is variability in the vapor concentration of the evaporating solvent above the wet coating. Even small differences in air flow above the wet coating cause significant changes in the vapor concentration above the wet coating resulting in non-uniformities in the dry layer due to spatial variations in the evaporation rate across and along the substrate.
  • One method known by those skilled in the art of high speed drying of a coated film is to blow a gas across the surface of the wet film so that evaporating solvent is continuously removed thus reducing the variability in the vapor concentration above the wet coating.
  • perovskite solutions typically have very low viscosity, e.g., less than 10 centipoise (viscosity changes with applied shear), due to the nature of the dissolved solids and the limited selection of useful solvents and additives.
  • the low viscosity of perovskite solutions causes blow marks in the dry layer when a gas is blown across the surface of the wet solution. Non-uniformity in the dry layer caused by blow marks makes the layer non-functional because discontinuities become electrical shorts in photovoltaic devices. Thinner wet laydowns reduce the non-uniformities caused by blowing air across the film but, as previously discussed, a relatively thick wet laydown is required when making a high speed deposition of perovskite solution.
  • a third reason for the variability in the dry perovskite layer is due to de wetting of the perovskite solution from the flexible multilayer substrate 60, which causes holes to form in the perovskite layer that severely degrade the performance of the completed perovskite device.
  • Carrier transport layers used in perovskite devices may be hydrophobic to improve device performance and most perovskite solutions tend to poorly wet the hydrophobic carrier transport layers. Perovskite solution dewetting is exacerbated by depositing thinner layers of perovskite solution and by increasing the drying time.
  • a novel perovskite solution has been formulated using a large proportion (e.g., at least 50 weight percent of total solvent, preferably at least 75 weight percent of total solvent, more preferably at least 90 weight percent of total solvent) of a low boiling point (e.g., less than 150 degrees Celsius, preferably less than 135 degrees Celsius) solvent.
  • a low boiling point solvent can be made to evaporate quickly from the perovskite solution after deposition on a substrate thus minimizing movement of the crystals that form as the perovskite solution dries. Solvents that do not strongly coordinate with the perovskite precursors further enable short annealing times.
  • Alcohol based solvents have been identified that do not strongly coordinate with the perovskite precursors, provide the proper solubility of the inorganic precursors, and have been shown to produce a perovskite solution that is stable for use in high volume manufacturing of perovskite layers and photovoltaic devices.
  • Examples of alcohol-based solvents suitable for use at high proportions in the perovskite solution include 2-methoxyethanol, 2-ethoxy ethanol, 2-butoxyethanol, 2-isopropoxyethanol, methanol, propanol, butanol, and ethanol. Mixtures of solvents are envisioned for use in the perovskite solution to tune the evaporation profile to further optimize the drying process.
  • Suitable solvent additives useful for modifying evaporation rate of the solvent include dimethylformamide, acetonitrile, dimethyl sulfoxide, N-methyl-2-pyrrolidone, dimethylacetamide, gamma- butyrolactone, phenoxy ethanol, acetic acid, and urea.
  • the preferred perovskite solution is formulated with greater than 30 percent by weight of solvent (e.g., 30-82 percent by weight) and at least 18 percent by weight of solids (e.g., 18-70 percent by weight, preferably 25-60 percent by weight or 30-45 percent by weight), where the total solids concentration of the perovskite solution is between 30 percent and 70 percent by weight of its saturation concentration at the provided solution temperature.
  • the preferred provided solution temperature is between 20 and 50 degrees Celsius.
  • the preferred solvent is an alcohol and has a boiling point less than 135 degrees Celsius.
  • the preferred solvent is 2-methoxyethanol, which has a boiling point of 125 degrees Celsius.
  • the disclosed perovskite solution formulations have the advantage of providing perovskite solutions that are stable at convenient handling and storage temperatures of, e.g., from 20 to 50 degrees Celsius and in particular typical room temperatures of from 20 to 25 degrees Celsius, and which can be used to manufacture a uniform Perovskite layer at high speed thereby enabling low cost production of high efficiency solar cells with low equipment costs.
  • Uniform perovskite layers have been made at high production speeds with the novel drying method and perovskite solution. However, it has been found that the time required for the perovskite solution to form homogeneous nuclei and grow may be longer than the time required to evaporate the low boiling point solvent in such a way as to produce a uniform perovskite layer. A uniform perovskite layer with optimum sized crystals is needed to make perovskite devices with high photovoltaic energy output. A crystal growth modifier added to a perovskite solution with a low boiling point solvent have been found that optimize the performance of perovskite photovoltaic devices.
  • a crystal growth modifier is defined as an additive that either alters the amount of time for homogeneous crystal growth or alters the rate of homogeneous crystal growth when drying a perovskite solution.
  • crystal growth modifiers that are especially useful in perovskite solutions for making high performance perovskite layers include dimethyl sulfoxide, N-methyl-2-pyrrolidone, gamma-butyrolactone, 1,8-diiodooctane, N-cyclohexyl-2-pyrrolidone, water, dimethylacetamide, acetic acid, cyclohexanone, alkyl diamines, and hydrogen iodide.
  • a preferred concentration of crystal growth modifier is less than about 10 percent by weight of the coating solution (e.g., 0.01 to 10 percent by weight).
  • a more preferred concentration of crystal growth modifier is less than about 2 percent by weight of the coating solution (e.g., 0.01 to 2 percent by weight).
  • a crystal grain boundary modifier is defined as an additive that improves the quality of the grain boundary, for example be altering the electrical properties of the perovskite crystal grain boundary or reducing trap states at perovskite crystal grain boundary interfaces.
  • crystal grain boundary modifiers that are especially useful in perovskite solutions for making high performance perovskite layers include choline chloride, phenethyl amine, hexylamine, 1-a- phosphatidylcholine, polyethylene glycol sorbitan monostearate, sodium dodecyl sulfate, Poly(methyl methacrylate), Polyethylene glycol, pyridine, thiophene, ethylene carbonate, propylene carbonate, fullerenes, polypropylene carbonate), and didodecyldimethylammonium bromide.
  • a preferred concentration of crystal grain boundary modifier is less than about 2 percent by weight of the coating solution (e.g., 0.01 to 2 percent by weight).
  • a more preferred concentration of crystal grain boundary modifier is less than about 0.2 percent by weight of the coating solution (e.g., 0.01 to 0.2 percent by weight).
  • Examples of inorganic perovskite precursors for making perovskite solutions include lead (II) iodide, lead (II) acetate, lead (II) acetate trihydrate, lead (II) chloride, lead (II) bromide, lead nitrate, lead thiocyanate, tin (II) iodide, rubidium halide, potassium halide, and cesium halide.
  • Examples of organic perovskite precursors for making perovskite solutions include methylammonium iodide, methylammonium bromide, methylammonium chloride, methylammonium acetate, formamidinium bromide, and formamidinium iodide.
  • the organic perovskite precursor material has a purity greater than 99 percent by weight and the inorganic perovskite precursor has a purity greater than 99.9 percent by weight.
  • the inorganic perovskite precursor contains a metal cation and preferred metal cation is lead. In the preferred
  • the molar ratio of organic perovskite precursor material to inorganic perovskite precursor material is between one and three.
  • the perovskite solution comprises an organic perovskite precursor material, an inorganic perovskite precursor material, and a solvent wherein the amount of solvent is greater than 30 percent by weight and the perovskite solution has a total solids concentration by weight that is between 30 percent and 70 percent of the perovskite solution’s saturation concentration at the provided solution temperature (i.e., temperature the solution is maintained at prior to deposition of the solution onto the flexible substrate.
  • the solvent may comprise one or more alcohols and the preferred provided solution temperature is between 20 and 50 degrees Celsius. In further preferred embodiments, it is preferred to have an amount of alcohol that is less than 50 percent by weight and a total solids concentration greater than 35 percent by weight.
  • the perovskite solution has an amount alcohol that is greater than 50 percent by weight and a total solids concentration less than 40 percent by weight. In another preferred embodiment, the perovskite solution has a total solids concentration between 30 and 45 percent by weight and an amount of 2-methoxy ethanol that is greater than 55 percent by weight.
  • perovskite crystals or the intermediate precursor phase for hybrid perovskite crystals form.
  • the intermediate phase is a crystal, adduct, or mesophase that is not the desired final crystal lattice, which is ABX3.
  • the intermediate phase if present, is converted to the desired final crystal lattice by annealing. This formation process has been found to be highly sensitive to variations in the solvent vapor concentration above the wet layer and to convective flow in the wet layer of perovskite solution.
  • a novel multistep method has been developed to form a uniform and functional perovskite layer at high speed.
  • FIG. 2a, 2b, 2c, and 2d illustrate in cross sections the formation of the perovskite layer on a portion of a multilayer flexible substrate 60 after important steps in embodiments of the disclosure.
  • FIG. 2a shows the layer of perovskite solution 64a on a flexible multilayer substrate 60 immediately after the deposition of the perovskite solution.
  • the flexible multilayer substrate 60 comprises a flexible support 61, a first conducting layer 62, and a first carrier transport layer 63.
  • the flexible support is the first conducting layer.
  • FIG. 2b shows a layer of the partially dry perovskite solution 64b on the flexible multilayer substrate 60 after a first drying step, hence the thickness of the layer of partially dry perovskite solution 64b is less than the thickness of the layer of perovskite solution 64a shown in FIG. 2a.
  • FIG. 2c shows an immobile layer of perovskite crystals or intermediate phases 64c on a flexible multilayer substrate 60 after a second drying step hence the thickness of the immobile layer perovskite crystals or intermediate phases 64c is less than the thickness of the layer of the partially dry perovskite solution 64b shown in FIG. 2b.
  • FIG. 2d shows the completed perovskite layer 64d on the flexible multilayer substrate 60 after an annealing step.
  • Examples of materials comprising the flexible support 61 include polyethylene terephthalate (PET), thin flexible glass such as Coming® Willow®
  • the preferred thickness of the flexible support 61 is in range from 25 to 200 microns. When metal foil is used the preferred thickness of the metal foil is between 5 and 50 microns.
  • Examples of materials comprising the first conducting layer 62 when used as the window for the photovoltaic device include transparent and semitransparent electrodes based on metal-nanowires and metal thin-films (see J. Mater. Chem. A,
  • metal mesh and metal grid electrodes made with metal nanoparticles, particulate metal paste, and/or electroplating;
  • PEDOT Poly(3,4-ethylenedioxythiophene)
  • PDOT poly(3,4- ethylenedioxythiophene):polystyrene sulfonate
  • doped and undoped metal oxides such as tin oxide (doped with indium or fluorine), molybdenum oxide, and zinc oxide (doped with aluminum).
  • a metal foil is preferred when the first conducting layer 62 is not on the window side.
  • the metal foil can be made from a wide range of metals but is preferred to be selected from the group consisting of copper, nickel, or stainless steel.
  • the metal foil may have more than one layer of metal such as copper coated with nickel or tin.
  • the metal foil may also be part of a laminate structure and include plastic layers such as PET or polyimide and an adhesive interlayer.
  • Examples of materials comprising the first carrier transport layer 63 and the second carrier transport layer 65 include poly(triaryl amine) (also known as Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]), poly-(N-vinyl carbazole), PEDOT complex, Poly(3-hexylthiophene), Spiro-MeOTAD (also known as
  • Carrier transport layers can be hole transport layers or electron transport layers depending on the desired structure of the solar cell, e.g. NIP or PIN. Many other carrier transport materials are known by those skilled in the art and are envisioned as possible materials for this disclosure.
  • FIG. 3 shows a schematic of an exemplary R2R deposition and drying device 100 that will be used to describe preferred embodiments of the disclosure. Additional configurations can be adapted to enable the multistep process of the disclosure by those skilled in the art.
  • a flexible multilayer substrate 60 is unwound from a unwind roll 10 and threaded through a deposition (and first drying step) section 20, a fast drying (second drying step) section 30, a long duration heating section 40, and a short duration heating section 50, then wound onto a rewind roll 12.
  • a deposition (and first drying step) section 20 a fast drying (second drying step) section 30, a long duration heating section 40, and a short duration heating section 50, then wound onto a rewind roll 12.
  • Other components in R2R deposition and drying devices known in the industry are considered useful for this disclosure but are not shown in FIG. 3.
  • a cooling section (not shown) may be useful prior to the rewind roll 12.
  • the direction of movement of the flexible multilayer substrate 60 through the R2R deposition and drying device 100 is identified by the arrows in the unwind roll 10 and the rewind roll 12.
  • a surface treatment device 14 conditions the surface of the flexible multilayer substrate 60 prior to deposition of the perovskite solution.
  • Surface treatment devices include corona discharge, ozone (created, for example, with ultraviolet radiation), and plasma.
  • Surface treatment devices can operate in ambient air, conditioned air (where temperature and relative humidity are controlled), oxygen, or inert gas such as nitrogen or argon.
  • the deposition (and first drying step) section 20 of the R2R deposition and drying device 100 includes one or more conveyance rollers 24 to direct the path of the flexible multilayer substrate 60 so that it is correctly presented to the deposition device 21 as well as correctly conveyed through the deposition section 20.
  • Conveyance rollers, tensioning rollers, and web guidance rollers are typically used throughout deposition and drying devices to aid in conveying flexible substrates, controlling tension and position.
  • a conveyance roller 13 is shown prior to the rewind roll 12 and conveyance rollers 41a-e are shown in the long duration heating section 40. To simplify FIG. 3 additional rollers are not shown.
  • Conveyance rollers may include air bearings to minimize or eliminate contact with the flexible multilayer substrate 60. Air flotation methods (not shown) known by those skilled in the art may also be used to minimize or eliminate contact between conveyance rollers and the flexible multilayer substrate 60.
  • the deposition device 21 that deposits a layer of perovskite solution comprising a solvent and perovskite precursor material to the flexible multilayer substrate 60 can be any number of known deposition devices but is preferred to be based on a slot die or gravure system (direct, reverse, or offset) deposition device. Other deposition devices envisioned for use in the disclosure include spray, dip coat, inkjet, flexographic, rod, and blade.
  • the perovskite solution is supplied to the deposition device 21 by methods and devices known by those skilled in the art (not shown).
  • the deposited perovskite solution layer is partially dried in section 20 in a first drying step by removing a first portion of solvent from the deposited solution while heating the deposited solution to a coated layer temperature.
  • the temperature of the perovskite solution and the coating device is preferably controlled by a temperature controller (not shown).
  • the setpoint for the temperature of the perovskite solution 64a deposited on the multilayer substrate 60 depends on the formulation of the perovskite solution.
  • the preferred temperature range for the heated deposited perovskite solution in the first drying step is between 30 and 100 degrees Celsius and a more preferred temperature range is between 35 and 60 degrees Celsius.
  • the thickness of the perovskite solution 64a initially deposited on the flexible multilayer substrate 60 is preferably less than 10 microns to minimize nonuniformities created by convective flow in the coated layer and greater than 2 microns to enable sufficient wetting of the perovskite solution 64a with the flexible multilayer substrate 60.
  • a backing roller 22 or set of rollers is used to set the engagement, gap or load to the deposition device 21.
  • the amount of air flow around the wet coating on the multilayer substrate 60 can optionally be controlled by constraining the movement of air above the wet coating with an air flow control device 27 such as screens, baffles or plenums.
  • the temperature and humidity of deposition section 20 may be controlled by an environmental controller 25a to optimize the coating and drying conditions in deposition section 20.
  • Optional control of the temperature of backing roller 22 is envisioned as well as control of the temperature of the flexible multilayer substrate prior to and subsequent to the deposition device 21 as depicted by plenums 23a and 23b, however, heated rollers, or heated fixed curved surfaces are also envisioned to control the temperature of the flexible multilayer substrate with conductive heating.
  • Backing roller 22 can act as a substrate heating device that heats the flexible multilayer substrate.
  • the backing roller 22 can have fluid flowing through it to maintain a preset temperature. This type of roller is sometimes called a jacketed roller.
  • the preferred range that a substrate heating device heats the flexible multilayer substrate to prior to depositing the layer of perovskite solution is between 30 and 100 degrees Celsius.
  • the flexible multilayer substrate 60 enters a fast-drying section 30 with the wet coating of the perovskite solution on the flexible multilayer substrate 60 that was applied by deposition device 21.
  • the first drying step is defined by the removal of a first portion of perovskite solution in the region between the deposition device 21 and the fast-drying section 30. The amount of solvent removed in the first drying step is an important factor in making a uniform coating.
  • This first drying step is affected by: the length of the first drying region, which is the distance between the deposition location 26 and the entrance of the fast-drying section 30; the temperature of deposition section 20, the temperature, speed, surface energy, and surface area of the flexible multilayer substrate 60; the amount of air flow around the wet coating of the perovskite solution on the flexible multilayer substrate 60 in the first drying region; and the formulation of the perovskite solution.
  • the preferred temperature of the area around the flexible multilayer substrate 60 and the perovskite solution is between 30 and 100 degrees Celsius during the first drying step.
  • the fast-drying section 30 defines a second drying step where a second portion of the solvent from the perovskite solution is removed, where the second drying step has a higher rate of solvent evaporation than the first drying step.
  • Any suitable device that causes rapid solvent removal from the wet coating can be used and may include a non-contact drying device 31 or a contact drying device 32 where contact is defined by physically contacting the flexible multilayer substrate.
  • Non-contact drying devices include air knives, infrared heaters, microwave heaters, convection ovens, Rapid Thermal Processors, and high energy photonic devices such as Xenon lamps.
  • Contact drying devices include conduction heaters such as heated rollers or station curved plates that contact the side of the web opposite the wet coating.
  • a non-contact drying device 31 used in the preferred embodiment of the disclosure is an air knife that blows gas, such as air or nitrogen, across the surface of the coating to lower the solvent vapor pressure and quickly remove the evaporating solvent.
  • the temperature of the gas is optionally controlled (not shown).
  • Some non-contact drying devices may benefit by the use of a nearby backing roller or rollers to control the spacing to the non-contact device 31 or to aid in drying the perovskite solution.
  • the temperature and humidity of the fast-drying section 30 may also be controlled by an environmental controller 25b to optimize the conditions of the second drying step.
  • the second drying step causes a conversion reaction in the perovskite solution that is induced by the rapid evaporation of the solvent from the solution causing saturation of the solids and crystal formation or formation of an intermediate phase.
  • the conversion reaction is typically readily visually apparent as it changes the color or optical density of the perovskite solution.
  • the degree of color change and change in optical density of the perovskite solution depends on the type and quantity of perovskite precursors that are present in the deposited perovskite solution. In order to create a uniform perovskite layer the conversion reaction must be fast in the second drying step so that the movement of the crystals is minimized as they are formed.
  • the conversion reaction that occurs in the second drying step causes the perovskite solution to have a large reduction in the transmission of visible light.
  • the percent transmission of visible light through the perovskite solution due to the conversion reaction in the second drying step is reduced by at least a factor of 2.
  • the percent transmission of visible light is defined by the amount of visible light leaving the sample divided by the amount of visible light entering the sample and can be measured by known methods such as directing white light on the deposited perovskite solution both prior to entering and after exiting the second drying location.
  • the percent transmission of visible light is determined by measuring the visible light intensity both entering and exiting the flexible multilayer substrate at the two locations. If the flexible multilayer substrate is opaque then a reflection measurement can be used to determine percent transmission of visible light through the perovskite solution.
  • the air knife When an air knife is used as the drying device, the air knife first acts on the perovskite solution at the focal point of the air flow directed to the perovskite solution residing on the multilayer substrate, which is defined by the intersection of a line drawn from the source of the air flow to the flexible multilayer substrate where the angle of the line is such that the line follows the air flowing from the air knife.
  • the location where the drying device acts on the perovskite is defined by the location where a significant portion of the optical radiation first strikes the perovskite solution, i.e., more than 5 percent of the optical energy has impinged on the perovskite solution out of the total amount that impinges on the perovskite solution from the optical device.
  • the temperature of the layer of perovskite solution 64b can be increased to speed the evaporation rate in the second drying step.
  • the preferred temperature in the area around the flexible multilayer substrate and the perovskite solution is greater than 30 degrees Celsius during the second drying step.
  • the dwell time of the first drying step is also important to obtaining a uniform coating at high speed. If the first drying step is too fast then convective flow in the layer of perovskite solution 64a creates artifacts, such as mottle, in the completed perovskite layer 64d. In addition, enough of the solvent must be removed in the first drying step so that the layer of perovskite solution can be dried quickly in the second drying step. If the first drying step does not remove enough solvent prior to the second drying step then nonuniformities in the coating, such as blow marks, are formed in the perovskite layer during the second drying step.
  • the first drying step has a dwell time that is at least 5 times longer than the second drying step dwell time, preferably at least 10 times longer.
  • the amount of solvent and the total solids concentration at the end of the first drying step can be measured by monitoring the wet thickness with a low coherence interferometer mounted at the end of the first drying step and calculating the perovskite solution total solids concentration and amount of solvent using the known the initial thickness and total solids concentration of the perovskite solution.
  • the amount of solvent remaining after the second drying step should be less than 10 percent of the initial amount of solvent, and preferably less than 5 percent of the initial amount of solvent.
  • the first drying step increases the total solids concentration of the perovskite solution to at least 75 percent of its saturation concentration (measured in weight percent solids), and more preferably to at least 90 percent of its saturation concentration, so that the subsequent conversion of the solution to a thin film of immobile crystals can occur rapidly in the second drying step.
  • the perovskite solution has changed from a solution or colloidal suspension to a layer comprised of immobile perovskite crystals or intermediates.
  • an additional annealing step is typically required.
  • the function of the annealing step can include the removal of residual solvents, the removal of excess volatile perovskite solution components, the growth of perovskite crystals, a dissolution-recrystallisation process (Ostwald ripening effect) of the perovskite crystals, conversion of intermediates to perovskite crystals, and changes in perovskite crystal boundaries.
  • the flexible multilayer substrate is conveyed over a series of conveyance rollers 41a-41e.
  • the entire structure of the long duration heating section 40 is enclosed to maintain a consistent temperature and air flow that is maintained by the environmental controller 25 c.
  • the annealing time of the layer of immobile perovskite crystals or intermediates 64c is important for producing high performance photovoltaic devices.
  • the annealing step may include heating the Perovskite layer to a temperature greater than 90 degrees Celsius for at least 30 seconds.
  • a flexible support 61 that can withstand high temperatures without distorting, such as thin flexible glass, metal foil, polysulfone, and polyimide, increasing the temperature of the long duration heating section 40 of FIG. 3 can reduce the required time to make a high performance perovskite layer.
  • the preferred temperature of the area around the flexible multilayer substrate and the perovskite layer is between 120 and 300 degrees Celsius during the annealing step.
  • the area around the flexible multilayer substrate and the perovskite layer is preferred to be between 90 and 125 degrees Celsius during the annealing step to minimize distortion of the flexible support 61.
  • a rapid annealing device can be employed to reduce the length of the heating section or to increase the production speed when using some perovskite formulations.
  • One method to reduce the long duration heating time is to rapidly heat one or more of the thin film coatings 62, 63, and 64c of the flexible multilayer substrate 60 to high temperature for a short duration (FIG. 2c). If the thin film coatings are heated directly without significantly heating the flexible support 61 then it is even possible to make high performance devices on low temperature flexible support 61 without the need for a very long oven.
  • the low temperature flexible support 61 is typically more than 150 times thicker than the thin film coatings 62, 63, and 64c.
  • FIG. 3 shows that the flexible multilayer substrate is conveyed from the long duration heating section 40 to the short duration heating section 50.
  • Short duration heating section 50 contains a short duration heater 51, such as a Rapid Thermal Processing unit or a high energy photonic device, e.g. a Xenon lamp.
  • a backing roller 52 or set of rollers can be optionally used to set the gap to the short duration heater 51.
  • the temperature and humidity of the short duration heating section 50 may also be controlled by an environmental controller 25d to optimize the conditions of the short duration heating section 50.
  • the long duration heating section 40 is eliminated and only the short duration heating section 50 is used.
  • both the long duration heating section 40 and the short duration heating section 50 are used.
  • only the long duration heating section 40 is used.
  • the flexible multilayer substrate 60 moves at nearly a constant speed through the R2R deposition and drying device 100 (FIG. 3).
  • a first location is defined by the region where the perovskite solution is deposited on the flexible multilayer substrate 60 by the deposition device 21.
  • a second location is defined by the region between the deposition device 21 and the fast-drying section 30.
  • a third location is defined as the fast-drying section 30.
  • a fourth location is defined as the region where the perovskite layer is heated in the annealing step by the annealing device.
  • the fourth location in Fig. 3 is the long duration heating section 40 and may include the region in the optional short duration heating section 50.
  • the flexible multilayer substrate 60 in the R2R deposition and drying device 100 is preferred to move at a speed greater than 5 meters per minute and more preferred to be greater than 10 meters per minute as it moves from a first location to a second location, and from the second location to a third location.
  • the perovskite layer is heated by an annealing device in an annealing step at the fourth location, wherein the flexible multilayer substrate is preferred to move a speed greater than 5 meters per minute and more preferred to move at a speed greater than 10 meters per minute from the third location to the fourth location.
  • annealing devices for use in the annealing step include a convection oven, a Rapid Thermal Processor, a photonic device (e.g. an infrared radiation source or a xenon lamp), a heated roller, and a stationary heated curved surface.
  • the flexible multilayer substrate is moving at a constant speed from the first location to the second location, and moving at the same constant speed from the second location to the third location, and the second drying step causes a conversion reaction in the perovskite solution that changes the color of the perovskite solution.
  • Methods and devices are envisioned to contain and control particulate contaminates for the entire R2R deposition and drying device 100 or for one or more of the sections 20, 30, 40, and 50.
  • Devices and methods to clean particulates from the flexible multilayer substrate include forced air, sticky rollers, and electrical discharge devices.
  • Devices and methods to clean the air and to maintain specified clean room conditions include forced air through HEPA filters and positive pressure in enclosures.
  • Methods and devices to remove and condition solvent vapors are envisioned but not shown in FIG. 3 nor are devices to remove unwanted gases or byproducts such as ozone and nitric oxides.
  • Static control devices are commonly used in devices that convey flexible webs but are not shown in FIG. 3.
  • FIG. 4 shows a schematic of an exemplary multi-station R2R deposition and drying device 200 for roll-to-roll printing a photovoltaic device on a flexible substrate that will be used to describe preferred embodiments of the disclosure.
  • a station of the multi-station R2R deposition and drying device 200 is defined as comprising a deposition section but other sections and devices may be part of the station. Additional configurations can be adapted to enable the multistep process of the disclosure by those skilled in the art to make some or all layers of perovskite devices, especially perovskite solar cells. While FIG. 4 shows five stations, more or less than five stations are envisioned for variations on preferred embodiments of the disclosure.
  • a multi-station R2R deposition and drying device with three stations (not shown) could be used to apply a first carrier transport layer, a perovskite absorber layer, and a second carrier transport layer in succession on top of a flexible substrate having a first electrode layer and a support layer.
  • a multi station R2R deposition and drying device with four stations (not shown) where the first electrode layer is formed on the flexible substrate in the first station of the multi station R2R deposition and drying device prior to the deposition of the first carrier transport layer.
  • the device is supplied with a flexible substrate having only a support layer.
  • the fourth station could be used to apply a second electrode layer on to the second carrier layer.
  • a multi-station R2R deposition and drying device with more than five stations is envisioned to make photovoltaic devices that require additional layers that improve the performance or functionality of the photovoltaic devices.
  • a flexible support 61 is unwound from a unwind roll 10 and threaded through five deposition sections 20a-e and five long duration heating sections 40a-e, in a continuous inline process to make a perovskite device 67.
  • the direction of movement of the flexible substrate 61 through the multi-station R2R deposition and drying device 200 is identified by the arrows adjacent to the unwind roll 10 and the rewind roll 12. Additional devices after each deposition section or long duration heating section are envisioned and some are shown in FIG.4 and described below.
  • Each deposition section 20a-e deposits a functional solution on to the flexible support 61 at the associated deposition location 26a-e with a deposition device 21a-e.
  • Each long duration heating section 40a-e heats the functional solution deposited by the associated deposition device to dry, cure, anneal, and/or sinter the functional solution.
  • process setpoints for each long duration heating section 40a-e are different as they are optimized for the solution that is deposited by the associated deposition device.
  • the process configurations and setpoints for each deposition section 20a-e may also be different from each other.
  • Deposition section 20a deposits a first electrode solution on the flexible support 61 with a first electrode deposition device 21a.
  • Long duration heating section 40a dries and sinters the first electrode solution to form a first electrode layer.
  • the flexible substrate with the first electrode layer then travels to the deposition section 20b where a first carrier transport solution is deposited on the first electrode layer with a first carrier transport deposition device 21b.
  • Long duration heating section 40b dries and sinters the first carrier transport solution to form a first carrier transport layer.
  • the flexible substrate with the first electrode layer and the first carrier transport layer then travels to the deposition section 20c where a perovskite solution is deposited on the first carrier transport layer with a perovskite solution deposition device 21c.
  • a first portion of the initial amount of solvent in the deposited perovskite solution is removed in section 20c in a first drying step, similarly as described for section 20 in FIG. 3.
  • the flexible substrate travels through a second drying step fast drying section 30, where a second portion of the initial amount of solvent in the deposited perovskite solution is removed. Note that the description of the fast drying section appears above in the description of FIG.
  • the second drying step causes a conversion reaction in the perovskite solution that is induced by the rapid evaporation of the solvent from the solution causing saturation of the solids and crystal formation or formation of an intermediate phase.
  • Long duration heating section 40c further dries and anneals the coated perovskite solution to form a perovskite layer.
  • the flexible substrate with the first electrode layer, the first carrier transport layer, and the perovskite layer then travels to the deposition section 20d where a second carrier transport solution is deposited on the perovskite layer with a second carrier transport deposition device 21 d.
  • Long duration heating section 40d dries the second carrier transport solution to form a second carrier transport layer.
  • the flexible substrate with the first electrode layer, the first carrier transport layer, the perovskite layer, and the second carrier transport layer then travels to the deposition section 20e where a second electrode solution is deposited on the second carrier transport layer with a second electrode deposition device 21 e.
  • Long duration heating section 40e dries the second electrode solution to form a second electrode layer.
  • the flexible substrate with the five functional layers is then wound onto a rewind roll 12.
  • Laser etching of thin films is known in the art and used here to create a monolithic photovoltaic device as part of the inline continuous manufacturing process.
  • the flexible substrate travels through a laser etch unit 70a.
  • the flexible substrate travels through a laser etch unit 70d.
  • the flexible substrate travels through a laser etch unit 70e.
  • Each laser etch unit contains a laser device 71a, d,e, and a laser etch backing roller 72a, d,e.
  • the laser etch backing rollers 72a,d,e are used to ensure that the flexible support 61 is in a known location.
  • a vision system (not shown) can be incorporated in one or more of the laser etch units 70a, d,e to increase the accuracy of the location that the laser etches.
  • a control system (not shown) can be incorporated in one or more of the laser etch units 70a,d,e to position the laser spots based on data collected. Feed forward and feedback may be used in the control system.
  • Laser etch unit 70a removes a portion of the first electrode layer.
  • Laser etch unit 70d removes a portion of the second carrier transport layer, a portion of the perovskite layer, and a portion of the first carrier transport layer.
  • Laser etch unit 70e removes a portion of the second electrode layer, a portion of the second carrier transport layer, a portion of the perovskite layer, and a portion of the first carrier transport layer.
  • a surface treatment device 14 may be used to condition the of the flexible support 61 or one or more of the layers made on the flexible support 61 prior to entering each deposition section 20a-e, and environmental controllers may be used for some or all of the deposition sections 20a-e and long duration heating sections 40a-e.
  • conveyance rollers and backing rollers for R2R machines have been described above and only a small number of conveyance rollers 13a-e and backing rollers 22a-e are identified in FIG. 4.
  • Other conventional components in R2R deposition and drying devices are known in the industry are envisioned for use in the method of this disclosure but are not shown in FIG. 4.
  • a flexible multilayer substrate having a width of 25.4 cm was conveyed through a R2R deposition and drying device made by Polytype Converting for 3 trials at constant speeds of 30, 32, and 35 meters per minute.
  • the Polytype Converting machine was modified as described below to enable the multistep drying method of the disclosure.
  • the R2R deposition and drying device had an inline arrangement for conveying a continuous flexible substrate from an unwind roll through the following sections: a surface treatment device, a deposition and first drying step section, a second drying step fast drying section, and a long duration heating section.
  • the flexible multilayer substrate with the perovskite layer was wound on a rewind roll.
  • the flexible multilayer substrate had a polyester film as the flexible support, a thin layer of indium tin oxide as the first conducting layer, and poly(triaryl amine) as the first carrier transport layer.
  • the surface treatment device was a corona discharge device that treated the coating surface of the flexible multilayer substrate with ozone prior to the deposition section. In the deposition section a 4.5 micron thick wet laydown of perovskite solution was deposited on to the flexible multilayer substrate using a gravure cylinder in direct mode as the deposition device. The gravure cylinder was heated to a temperature of 40 degrees Celsius and maintained at that temperature while the perovskite solution was deposited.
  • the perovskite solution had 33 weight percent solids with an equal molar mixture of lead (II) iodide and methylammonium iodide and a liquid comprising 99.25 percent by volume of 2-methoxyethanol and 0.75 percent by volume of dimethyl sulfoxide.
  • the saturation concentration of the perovskite solution is 62 weight percent solids at 20 degrees Celsius.
  • the distance from the deposition location to the fast drying section was 1.4 meters and defines the region of the first drying step.
  • the first drying step included heating the substrate with a fixed curved surface 0.4 meters in length that contacted the backside of the moving flexible multilayer substrate across its entire width. The fixed curved surface was maintained at 73.6 degrees Celsius.
  • the second drying step occurring in the fast drying section, included an air knife that blew nitrogen out of a 75 micron wide slot on to the perovskite solution to increase the rate of solvent evaporation from the deposited perovskite solution relative to the first drying step.
  • the slot was positioned 1.5 cm from the moving substrate and ran across the width of the moving substrate.
  • the focal point of the air knife was positioned at the downstream end of the fixed curved surface at an angle of 20 degrees relative to the web, pointing away from the deposition location.
  • Nitrogen gas was supplied to the air knife at a flow rate of 40 standard cubic feet per minute.
  • the long duration heating section consisted of a convection oven 18 meters in length set to a temperature of 120 degrees Celsius.
  • a flexible multilayer substrate having a width of 15.2 cm was conveyed through a R2R deposition and drying device made by Eastman Kodak Company for 6 trials at the constant speeds of 11.9, 12.2, 12.5, 12.8, 13.1, and 13.4 meters per minute.
  • the R2R machine was modified as described below to enable the multistep drying method of the disclosure.
  • the R2R deposition and drying device had an inline arrangement for conveying a continuous flexible substrate from an unwind roll through the following sections: a deposition and first drying step section, a second drying step occurring in a fast drying section, and a long duration heating section.
  • the flexible multilayer substrate with the perovskite layer was wound on a rewind roll.
  • the flexible multilayer substrate had a polyester film as the flexible support, a thin layer of indium tin oxide as the first conducting layer, and poly(triaryl amine) as the first carrier transport layer.
  • a 4.5 micron thick wet laydown of perovskite solution was deposited on to the flexible multilayer substrate using a slot die as the deposition device.
  • the slot die was heated to a temperature of 50 degrees Celsius and maintained at that temperature while the perovskite solution was deposited.
  • the back side of the flexible support was also heated to a temperature of 50 degrees Celsius in the deposition section using a temperature controlled roller, and maintained at that temperature while the perovskite solution was deposited.
  • the perovskite solution had 33 weight percent solids with an equal molar mixture of lead (II) iodide and methylammonium iodide and a liquid comprising 99.25 percent by volume of 2-methoxyethanol and 0.75 percent by volume ofN-methyl-2-pyrrolidone with 0.4 milligrams per milliliter of 1-a-phosphatidylcholine as an additive.
  • the saturation concentration of the perovskite solution is 62 weight percent solids at 20 degrees Celsius.
  • the distance from the deposition location to the fast drying section was 1 meter and defines the region of the first drying step.
  • the first drying step included heating the substrate and deposited perovskite solution in a 0.7 meter section of an oven, over which a screen was positioned 3 cm above the moving web to limit air turbulence in the first drying step.
  • the oven was controlled to approximately 35 degrees Celsius.
  • the second drying step, occurring I the fast drying section included an air knife that blew nitrogen out of a 75 micron wide slot on to the perovskite solution to increase the rate of solvent evaporation from the deposited perovskite solution relative to the first drying step.
  • the slot was positioned 1.5 cm from the moving substrate and ran across the width of the moving substrate.
  • the air knife was immediately downstream of the first drying step, fixed at an angle of 25 degrees relative to the web, pointing away from the deposition location. Nitrogen gas was supplied to the air knife at a flow rate of 40 standard cubic feet per minute.
  • the long duration heating section consisted of a convection oven 11.88 meters in length set to a temperature of 120 degrees Celsius.
  • the trial that produced the most uniform perovskite layer was achieved with the trial run at 12.8 meters per minute.
  • a second transport layer and a second conducting layer were subsequently deposited onto the perovskite layer to make functioning photovoltaic devices with power conversion efficiency exceeding 10 percent.
  • the multistep drying method described here has been found to produce very uniform perovskite layers and enables reliable, high speed production of low cost, high efficiency perovskite devices. While the methods described here use roll- to-roll conveyance, a sheet fed system is envisioned for some of the embodiments where the substrate is provided to sections and devices in the form of a sheet.
  • Perovskite devices include electromagnetic radiation sensors, photovoltaic devices, and light emitting devices.
  • the invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

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Abstract

La présente invention porte sur un procédé de fabrication d'une couche de pérovskite, consistant à fournir un substrat souple ; à fournir une solution de pérovskite comprenant une quantité initiale de matériaux précurseurs de pérovskite et de solvant et une concentration totale en solides comprise entre 30 pour cent et 70 pour cent en poids de sa concentration de saturation ; à déposer la solution de pérovskite sur le substrat ; à éliminer une première partie du solvant de la solution de pérovskite déposée, et à augmenter la concentration totale en solides de la solution de pérovskite à au moins 75 pour cent de sa concentration de saturation au moyen d'une première étape de séchage ; et à éliminer une seconde partie du solvant de la solution de pérovskite déposée au moyen d'une seconde étape de séchage présentant un taux d'évaporation de solvant plus élevé qui provoque une saturation ainsi qu'une réaction de conversion dans la solution de pérovskite déposée menant à la formation de cristaux de pérovskite ou à la formation d'une phase intermédiaire de pérovskite, le temps de maintien de la première étape de séchage étant au moins 5 fois plus long que le temps de maintien de la seconde étape de séchage. L'invention concerne également un procédé en ligne continu permettant de produire des dispositifs photovoltaïques à grande vitesse, ainsi qu'une solution de pérovskite destinée à être utilisée dans la fabrication d'une couche de pérovskite uniforme à grande vitesse afin de permettre une production à faible coût de dispositifs pérovskite à rendement élevé.
PCT/US2020/034901 2019-05-30 2020-05-28 Procédé de fabrication d'une couche de pérovskite à grande vitesse WO2020243287A1 (fr)

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MX2021014434A MX2021014434A (es) 2019-05-30 2020-05-28 Metodo para hacer una capa de perovskita a alta velocidad.
EP20814928.6A EP3977529A4 (fr) 2019-05-30 2020-05-28 Procédé de fabrication d'une couche de pérovskite à grande vitesse
US17/615,142 US20220238807A1 (en) 2019-05-30 2020-05-28 Method of making a perovskite layer at high speed
CN202080052785.0A CN114514624A (zh) 2019-05-30 2020-05-28 高速制造钙钛矿层的方法
CA3142260A CA3142260A1 (fr) 2019-05-30 2020-05-28 Procede de fabrication d'une couche de perovskite a grande vitesse
KR1020217043326A KR20220054249A (ko) 2019-05-30 2020-05-28 고속으로 페로브스카이트 층을 제조하는 방법
JP2021570823A JP7519701B2 (ja) 2019-05-30 2020-05-28 ペロブスカイト層の高速製造方法

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US16/426,341 US11342130B2 (en) 2019-05-30 2019-05-30 Method of making a photovoltaic device on a substrate at high speed with perovskite solution
US16/426,191 2019-05-30
US16/426,191 US11108007B2 (en) 2019-05-30 2019-05-30 Method of making a perovskite layer at high speed
US16/426,341 2019-05-30
US16/426,439 2019-05-30
US16/426,439 US20200377532A1 (en) 2019-05-30 2019-05-30 Perovskite solution for making a perovskite layer at high speed

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Cited By (6)

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CN112614945A (zh) * 2020-12-16 2021-04-06 同济大学 具有沟槽阵列结构的微纳单晶柔性光电探测器及其制备
CN113845896A (zh) * 2021-09-10 2021-12-28 天津理工大学 曲面有机铵金属卤化物薄膜、制备方法、太阳能电池及应用
CN114188487A (zh) * 2021-12-10 2022-03-15 中国地质大学（北京） 利用含乙酸铵的反溶剂制备钙钛矿太阳能电池的方法
US20230119125A1 (en) * 2020-02-12 2023-04-20 Rayleigh Solar Tech Inc. High performance perovskite solar cells, module design, and manufacturing processes therefor
WO2023109072A1 (fr) * 2021-12-13 2023-06-22 中国华能集团清洁能源技术研究院有限公司 Système de solvant et procédé de préparation de photopiles en pérovskite
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CN112614945A (zh) * 2020-12-16 2021-04-06 同济大学 具有沟槽阵列结构的微纳单晶柔性光电探测器及其制备
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WO2023175466A1 (fr) * 2022-03-18 2023-09-21 Ricoh Company, Ltd. Élément de conversion photoélectrique, module de conversion photoélectrique, dispositif électronique et module de cellule solaire

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