WO2019100070A1 - Procédé et système pour cellule solaire à pérovskites avec structure en échafaudage - Google Patents

Procédé et système pour cellule solaire à pérovskites avec structure en échafaudage Download PDF

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Publication number
WO2019100070A1
WO2019100070A1 PCT/US2018/062088 US2018062088W WO2019100070A1 WO 2019100070 A1 WO2019100070 A1 WO 2019100070A1 US 2018062088 W US2018062088 W US 2018062088W WO 2019100070 A1 WO2019100070 A1 WO 2019100070A1
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Prior art keywords
layer
porous
transport layer
conducting
pvsk
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PCT/US2018/062088
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English (en)
Inventor
Matthew Robinson
Adam BURKETT
Alex GOVAERTS
Jimmy MEI
Rui LU
David Needleman
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Energy Everywhere, Inc.
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Publication of WO2019100070A1 publication Critical patent/WO2019100070A1/fr

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    • 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
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • 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
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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

  • PVSK perovskite
  • CaTi03 calcium titanium oxide
  • methylammonium lead halides which have a formula of CH 3 NH 3 PbX, where X is bromine, chlorine or iodine.
  • PVSK increases solar conversion efficiency compared to conventional silicon solar cells.
  • PVSK can reduce cost and weight and make flexible (non-rigid) solar cells.
  • PVSK can be formed on semiconductor materials using various techniques. Despite the progress made in solar cell technology, there is a need in the art for improved methods and systems related to PVSK solar cell technology.
  • the present invention relates generally to fabrication of semiconductor devices that incorporate one or more PVSK layers. More particularly, embodiments of the present invention relate to fabrication of photovoltaic cells (PVCs) in which one or more PVSK layers are formed in a PVC scaffold structure.
  • PVCs photovoltaic cells
  • the method may include: providing a first conducting layer; forming a first transport layer in electrical contact with the first conducting layer; forming a porous insulating layer in electrical contact with the first transport layer; forming a porous second transport layer in electrical contact with the porous insulating layer; forming a porous second conducting layer in electrical contact with the porous second transport layer; thereafter, performing a curing process at a temperature greater than 200 °C; and thereafter, forming a perovskite crystal structure in one or more of the porous insulating layer, the porous second transport layer, and the porous second conducting layer.
  • the substrate may be transparent.
  • the substrate may be an insulating substrate.
  • the substrate may be flexible.
  • the photovoltaic cell may include: a first conducting layer; a first transport layer in electrical contact with the first conducting layer; a porous insulating layer in electrical contact with the first transport layer; a porous second transport layer in electrical contact with the porous insulating layer; a porous second conducting layer in electrical contact with the porous second transport layer; and a perovskite crystal structure disposed in one or more of the porous insulating layer, the porous second transport layer, and the porous second conducting layer.
  • the substrate may be transparent.
  • the substrate may be an insulating substrate.
  • the substrate may be flexible.
  • the various embodiments provide a PVC scaffold structure that includes one or more porous layers fabricated to facilitate infiltration of the PVSK material into the scaffold structure. PVSK crystal can then be formed using a low temperature cure.
  • the scaffold structure provides additional support for the PVSK crystal structure formed therein.
  • a capping layer may form a barrier to prevent entry or exit of air and water vapor or other vapors from entering or exiting the PSC thereby enhancing the stability of the device.
  • FIG. 1 A illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in a p-i-n configuration according to an
  • FIG. 1B illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in an n-i-p configuration according to an embodiment of the present invention.
  • FIG. 1C illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material having a capping layer in a p-i-n configuration according to an embodiment of the present invention.
  • FIG. 2 illustrates a process flow of fabricating the scaffold structure and the infiltrated PVSK material according to an embodiment of the present invention.
  • FIG. 3 A illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in a p-i-n superstate configuration according to an embodiment of the present invention.
  • FIG. 3B illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in an n-i-p superstate configuration according to an embodiment of the present invention.
  • FIG. 4 illustrates a process flow for fabricating the scaffold structure and the infiltrated PVSK material in an superstate configuration according to an embodiment of the present invention.
  • FIG. 5 is a simplified band diagram for a semiconductor device according to an embodiment of the present invention.
  • FIG. 6A illustrates a simplified cross section of a PVC with a transparent conducting oxide layer formed on a porous transport layer according to an embodiment of the present invention.
  • FIG. 6B illustrates a plan view of a PVC with a porous TCO layer according to an embodiment of the present invention.
  • FIG. 7 illustrates a simplified process for fabricating a perovskite based
  • PVC photovoltaic cell
  • the present invention relates generally to fabrication of semiconductor devices that include a perovskite layer. More particularly, embodiments of the present invention involve methods and systems that form a photovoltaic cell (PVC) by forming a porous scaffold structure infiltrated with perovskite (PVSK) material.
  • PVC photovoltaic cell
  • PVSK perovskite
  • Some PVC fabrication processes are monolithic and generally begin by coating a layer of material onto a semiconductor substrate, then adding successive layers including a PVSK layer.
  • One method involves growing a crystalline PVSK layer by applying a solvent to a precursor solution, the precursor solution being spin-coated onto an underlying layer. Crystallization of the PVSK layer occurs at low temperatures relative to processing temperatures required to realize optimized properties of the transparent electrode and carrier selective layers needed in a PVC in addition to the PVSK. In order to have ideal properties, successive layers need to be vacuum deposited or solution deposited followed by heating to very high temperatures that are potentially incompatible with an earlier deposited PVSK layer.
  • PVSK is a relatively fragile material, being brittle, water soluble and heat sensitive. This has limited the choice and quality of materials that can be used in combination with PVSK, for example, the materials that can be coated on top of a given PVSK layer. Many materials used in traditional PVCs with desirable properties cannot be fabricated on top of a PVSK layer due to PVSK's sensitivity to the many solvents, chemicals, high temperature, and ion bombardment used in their fabrication. Accordingly, there is a need in the art for flexible fabrication techniques that permit different materials to be used in combination with PVSK in the PVC.
  • FIG. 1 A illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in a p-i-n configuration according to an embodiment of the present invention.
  • the PVC 100 is fabricated in a substrate configuration having p-i-n construction.
  • the device 100 is a photovoltaic cell comprising a first conducting layer 102, a first transport layer 110, a porous insulating layer 120, a porous second transport layer 130, and a porous second conducting layer 140.
  • additional layers can be formed between one or more layers such as a passivation layer, a capping layer, a barrier layer, and the like.
  • references to first and second transport layer of a cell can also be referring to a hole transport material or an electron transport material.
  • references herein utilize the transport layer nomenclature in reference to various figures, but it will be appreciated that transport layer can be referring to a carrier selective layer and/or a carrier selective tunnel barrier. Accordingly, the transport layer nomenclature utilized here is not intended to limit the scope of the present invention and is utilized merely for purposes of clarity.
  • one or more of the layers in device 100 can be porous to form a scaffold structure that can be infiltrated with a PVSK solution to form a PVSK crystal structure.
  • a precursor solution can be used to create a given layer using particle dispersion.
  • the insulating layer 120 can include large pores in order to fit a large volume of absorber material such as the PVSK solution.
  • the second transport layer 130 can be comprised of larger particles than the pore openings of the insulating layer 120.
  • the insulating layer 120 can be created using surfactants, solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, that is not cured out of the device 100 until after one or more layers are coated on the device 100 as required.
  • the first conducting layer 102 can be comprised of any electrically conducting material, for example, aluminum, copper, gold, silver, stainless steel, ITO, FTO, and the like. In some embodiments the first conducting layer 102 can serve as a substrate on which additional layers are formed.
  • the first conducting layer 102 can be a thin flexible metal foil that facilitates fabrication of a flexible device 100.
  • the first conducting layer 102 can operate as an electrode for the PVC.
  • an insulating layer and an additional conducting layer can be coupled to the front side 104 of the first conducting layer 102 to electrically isolate the first conducting layer from the entire PVC where monolithic integration is required.
  • an insulating layer can be coupled to the backside of the first conducting layer 102 to electrically isolate the first conducting layer 102 from the external environment or provide rigidity to facilitate spin-coating processes used to form additional layers.
  • an optional thin film such as a passivating layer can be deposited on the first conducting layer 102.
  • a first transport layer 110 can be formed on the first conducting layer 102.
  • the first transport layer 110 can be formed using a hole transport material.
  • the first transport layer 110 can include a tunnel barrier.
  • the hole transport material can be a p-type semiconductor configured to facilitate the movement of positive charge, i.e., "holes," in the first transport layer 110.
  • the first transport layer 110 can be fabricated using nickel oxide (NiOx), barium nickel oxide (BaNiOx) and/or another hole transport material.
  • the first transport layer 110 can be a dense hole transport material with zero percent or near zero percent porosity.
  • the thickness can be between 0.001 pm and 1.0 pm, in preferred embodiments, the thickness can be between 0.001 pm and 0.2 pm.
  • the first transport layer 110 can comprise two or more sub- layers.
  • the first sub-layer can be a dense layer of hole transport material coupled to the first conducting layer 102.
  • the second sub-layer on top of the first sub-layer can be a porous layer of hole transport material.
  • the porosity of the second sub-layer can vary from zero to 30 % porous.
  • the porous sub-layer facilitates contact between the PVSK crystal formed at the bottom of the insulating layer 120 and first transport layer 110.
  • the thickness can be between 0.001 pm and 1.0 pm, in preferred embodiments, the thickness can be between 0.001 pm and 0.10 pm.
  • the porous insulating layer 120 can be coupled to the first transport layer 110.
  • the porous insulating layer 120 can be an insulating ceramic.
  • Insulating ceramics include transition metal oxides such as alumina (AI2O3), zirconia (ZrCk), titania (T1O2), and the like.
  • the insulating layer 120 is sufficiently electrically insulating to prevent electrical contact between the first transport layer 110 and a second transport layer 130.
  • the insulating layer 120 can be porous to facilitate the infiltration of a PVSK solution into the porous insulating layer 120 and any porous layers coupled to the insulating layer 120 such as a second porous sub-layer of the first transport layer 110 or to make contact with a dense first transport layer 110.
  • the porosity can vary from 10 to 90 % porous; in preferred
  • the thickness for the insulating layer 120 can be 0.25 pm to 10 pm.
  • the preferred thickness for the insulating layer can vary from 0.5 mih to 5.0 mih and 1.0 mih to 3.0 mih depending on the absorbance of the PVSK crystal, the porosity of the insulating layer, and the degree to which recombination has been mitigated with passivation.
  • the second transport layer 130 can be formed on the insulating layer 120.
  • the second transport layer 130 can be formed using an electron transport material.
  • the second transport layer 130 can include a tunnel barrier.
  • the electron transport material can be an n-type
  • the second transport layer 130 can be fabricated using titanium oxide (TiOx), tin oxide (SnOx) and/or another electron transport material. In various embodiments the second transport layer 130 can be fabricated to be a porous layer.
  • the porosity can vary from 0 to 40 % porous. In some preferred embodiments, the porosity can vary between five and 10 %.
  • a porous second transport layer can be fabricated using, for example, but not limited to, a nanoparticle dispersion system, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and the like.
  • organometallic precursors and surfactants e.g., sol-gel
  • solvents, binders, dispersants, or other materials for example, but not limited to, polymer beads, and the like.
  • an appropriate gas can be used to form a corresponding crystal structure and doping density.
  • Surfactants, solvents, binders, dispersants, or other materials for example, but not limited to, polymer beads can be evaporated during the curing process leaving a porous material.
  • a porous second transport layer 130 facilitates the infiltration of a PVSK solution into the porous insulating layer 120 and into or up to the first transport layer 110.
  • the thickness for the second transport layer 130 can be between 0.02 pm to 1.0 pm. In some embodiments the preferred thickness is as thin as possible, or 0.02 pm, to reduce the resistance and recombination associated with the second transport layer 130.
  • the second transport layer can be thick enough to keep the filled PVSK crystal structure from touching the second conducting layer 140 when a capping layer (discussed further below) is used in device 100.
  • a second conducting layer 140 can be formed on the second transport layer 130.
  • the second conducting layer 140 can be a transparent conducting oxide (TCO).
  • TCO transparent conducting oxide
  • the second conducting layer 140 can be formed by, for example, sputtering, ALD, solution coating, or the like.
  • the second conducting layer 140 can be a porous TCO.
  • Transparent conducting oxides can include indium tin oxide (ITO), aluminum doped zinc oxide (ZnO:Al), indium doped zinc oxide (ZnO:In), and the like.
  • the second conducting layer 140 can be made porous using techniques, for example, but not limited to, dispersed nanoparticle precursors, solutions containing organometallic precursors and surfactants, solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, a surfactant templated metal oxide film system (e.g., sol-gel), and the like.
  • nanoparticles can sinter together leaving a void or pore.
  • an appropriate gas can be used to form a corresponding crystal structure and doping density.
  • Surfactants, solvents, binders, dispersants, or other materials for example, but not limited to, polymer beads, can be evaporated during the curing process leaving a porous material.
  • a porous second conducting layer 140 facilitates the infiltration of a PVSK solution into the second transport layer 130, the porous insulating layer 120, and the first transport layer 110.
  • the porosity can vary from 0 to 40 % porous. In some embodiments, 36% porosity represents random close packing of spheres in the second conducting layer 140.
  • the second conducting layer 140 can be as dense as possible while still being permeable to a PVSK solution, for example, the porosity can vary between five and 10%.
  • the thickness for the second conducting layer 140 can be between 0.02 pm to 5.0 pm. In some preferred embodiments, the thickness can be approximately 0.40 pm.
  • a dense second conducting layer 140 can be printed as a dense grid of TCO precursor to fabricate a dense TCO in most of the second conducting layer 140.
  • the grid can be formed with "doors" for the PVSK solution to infiltrate the transport layers and insulating layers.
  • a porosity of 5% to 10% can be achieved.
  • one or more bus bars 142 can be formed on the second conducting layer 140.
  • the one or more bus bars 142 can be formed using lithography, screen printing, flexographic printing, and the like.
  • the bus bars 142 can be cured at high temperatures before the PVSK crystal is formed on the device 100. High temperature deposition can be used to fabricate less expensive, higher quality bus bars formed of aluminum, copper, gold, silver, stainless steel, and the like.
  • porosity is not required if the grid is printed to facilitate the spreading of the PVSK solution underneath the grid lines.
  • the bus bars 142 can be printed at lower temperatures using materials such nickel paste, silver paste, and the like.
  • the one or more bus bars 142 can be a wire mesh.
  • the wire mesh can be inserted between a laminating sheet and the second conducting layer 140.
  • the laminating sheet can be placed on top of device 100 to electrically isolate the device.
  • the grid and laminating sheet can be held in place with, for example, a potting resin.
  • a PVSK crystal structure 144 is indicated by the plurality of points illustrated in FIG. 1 A.
  • the PVSK crystal structure 144 can be formed in the pores of device 100 by infiltrating one or more liquid solutions into the porous layers of device 100 using a method such as blade coating, slot die coating, capillarity coating, dip coating, drop casting, spin coating, and the like.
  • the liquid solution can be a PVSK solution or a PVSK melt. Once the solution has infiltrated the pores, device 100 can be cured at a low temperature to form the PVSK crystal structure.
  • porous layers facilitate the fabrication of a PVSK crystal structure 144 in the TCO, second conducting layer 140; the electron transport material, second transport layer 130; the insulating ceramic, insulating layer 120; and the porous sub- layer of the hole transport material, first transport layer 110.
  • FIG. 1B illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in an n-i-p configuration according to an embodiment of the present invention.
  • the PVC 152 is fabricated in a substrate configuration having n-i-p construction.
  • the device 152 illustrates a different structure from device 100 in FIG. 1 A because the electron and hole transport layers are in a different configuration.
  • Device 152 comprises a first conducting layer 102, an electron transport layer 150, a porous insulating layer 160, a porous hole transport layer 170, and a porous second conducting layer 140.
  • the layers can be formed using materials and methods discussed in relation to FIG. 1 A.
  • additional layers can be formed between one or more layers such as one or more passivation layers, a capping layer, a barrier layer, and the like.
  • the PVSK crystal structure 144 can be in contact with bus bars 142.
  • some bus bar 142 materials such as silver, can diffuse into PVSK when the temperature reaches to 70 °C.
  • a barrier layer between the porous layers and the electrode can be used to impede diffusion.
  • the barrier layer can be approximately 10 nm.
  • a barrier layer which has an oxygen deficiency property such as MoOx can be used.
  • a dense barrier layer between the second conducting layer 140 and the second transport layer 170 can block infiltration.
  • a capping layer can be used to form a dense layer on the upper layers and performs the functions of the capping layer and the barrier layer.
  • a capping layer can be formed on the PVSK crystal structure 144.
  • FIG. 1C illustrates a simplified cross section of a PVC 175 fabricated using a scaffold structure and an infiltrated PVSK material having a capping layer in a p-i-n configuration according to an embodiment of the present invention.
  • the PVC 175 is fabricated in a substrate configuration having p-i-n construction.
  • the first conducting layer 102, the first transport layer 110 including the dense first transport sub-layer 112, the porous insulating layer 120, and the porous second conducting layer 140 may be the same as described with respect to FIG. 1 A.
  • the second transport layer may include a porous second transport sub layer 130, for example a porous ETM layer formed on the porous insulating layer 120, and a dense second transport sub-layer 135, for example a dense ETM layer, formed on the porous transport sub-layer 130.
  • the dense ETM layer 135 may be formed from, for example, TiCh.
  • the porous second conducting layer 140 may be formed on the dense transport sub-layer 135.
  • a top electrode 142 may be formed on the porous second conducting layer 140.
  • the top electrode 142 may be a wire mesh or grid.
  • the wire mesh or grid may be formed from metal wires, for example, but not limited to, aluminum, copper, gold, silver, stainless steel, etc., and may have a thickness in a range of 10-30 pm.
  • the PVSK crystal structure 144 can be formed in the pores of device 175 by infiltrating a PVSK solution or a PVSK melt into the porous layers of device by one of the previously described methods.
  • the PVSK material may infiltrate the porous materials from
  • the top electrode 142 may include one or more bus bars formed on the second conducting layer 140.
  • the one or more bus bars can be formed using lithography, screen printing, flexographic printing, and the like.
  • the bus bars can be cured at high temperatures before the PVSK crystal is formed on the device 100. High temperature deposition can be used to fabricate less expensive, higher quality bus bars formed of aluminum, copper, gold, silver, stainless steel, and the like.
  • porosity is not required if the grid is printed to facilitate the spreading of the PVSK solution underneath the grid lines.
  • the bus bars can be printed at lower temperatures using materials such nickel paste, silver paste, and the like.
  • a capping layer 145 may be formed by infiltrating a suspension (e.g., sol-gel) or solution of particles, for example, but not limited to, AI2O3 nanoparticles, zirconium(II) oxide (ZrO) nanoparticles, or nanoparticles of another nonconductive oxide, into the spaces of the porous second conducting layer 140. Infiltration may be substantially halted by the dense second transport sub-layer 135.
  • the capping layer 145 may form a barrier to prevent entry or exit of air and water vapor or other vapors from entering or exiting the PSC thereby enhancing the stability of the device.
  • conductive oxide nanoparticles for example, but not limited to, ITO, indium gallium zinc oxide (IGZO), IZO, aluminum doped zinc oxide (AZO), or nanoparticles of another transparent conductive oxide, may be used as a material to form the capping layer 145.
  • the capping layer material may be a polymer, for example, but not limited to thermoplastic and thermoset polymers for example, but not limited to, poly(methyl methacrylate) (PMMA), epoxy, silicone, urethanes, or other polymer that are transparent at least in the absorption range of the PVSK absorber.
  • an encapsulating layer 150 may be formed over the top electrode 142 of device 175 to electrically isolate the device.
  • the encapsulating layer may be a polymer, for example, but not limited to, ethylene-co-vinyl acetate (EVA), polyolefin elastomer-based (POE) materials, or other similar materials.
  • FIG. 1C illustrates a PVC in a p-i-n configuration
  • embodiments are not limited to this implementation.
  • the PVC may be implemented in a n-i-p configuration without departing from the scope of the present disclosure.
  • the capping layer can use a solution, e.g., a capping material, to form one or more dense layers in or above the second transport layer.
  • a solution e.g., a capping material
  • the device can be coated with the capping material solution using technique such as blade coating, slot die coating, capillarity coating, dip coating, drop casting, spin coating, or similar method.
  • the capping material solution can infiltrate the porous second conducting layer 140. The infiltration may be substantially halted by the dense transport sub- layer 135.
  • these layers can still require a high temperature to obtain the ideal properties, however because the PVSK is below the capping layer and inside device 100, the heat would not decompose the PVSK.
  • the melting and recrystallization of the PVSK crystal structure 144 below the capping layer can be beneficial.
  • the layers below the intended capping layers must be free of volatile components.
  • the device 100 can be heated to high temperature prior to application of the PVSK and capping layers in order to remove all volatile components.
  • a resin can be coated onto the first transport layer after the pores of the device 100 have been infiltrated with the PVSK solution or the PVSK melt.
  • the PVSK solution or the PVSK melt is not filled to the top of the device 100, for example, a predetermined amount of about 10 % from the top can be left unfilled.
  • a resin can be used to fill the top 10 % of the porous structure. The resin can be mechanically abraded back to re-expose the upper transport layer.
  • a dense second conducting layer 140 comprising TCO, nanowire networks, or the like can be allied on top.
  • the capping layer can be formed using an oxide precursor solution in the second conducting layer 140 and heating to high temperature.
  • FIG. 2 illustrates a process flow for fabricating the scaffold structure and the infiltrated PVSK material according to an embodiment of the present invention.
  • the process flow 200 can be utilized to produce device 100.
  • the process flow 200 begins by providing a substrate, in some embodiments, a first conducting layer 102.
  • the first conducting layer 102 can be coated with a hole transport material precursor to form the first transport layer 110.
  • the first transport layer 110 can be fabricated to be a porous material.
  • the hole transport material can be deposited using, for example, but not limited to, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 144.
  • organometallic precursors and surfactants e.g., sol-gel
  • solvents e.g., binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 144.
  • oxides that can be used for the hole transport layer and generally require high curing temperatures (greater than 200 °C): NiOx, Cu:NiO, LiMgNiO, CuGaCb, CuO, C O, MC02O4, CuCrCk or Mg:CuCr02.
  • the curing temperatures for these oxides generally range from 300 °C to 600 °C and are relatively high in comparison to the melting or crystallization temperature of PVSK.
  • the first transport layer 110 can be coated with a ceramic precursor that can be cured to form the insulating layer 120.
  • the ceramic precursor can be applied using a technique such as blade coating, slot die coating, capillarity coating, dip coating, drop casting, spin coating, or other deposition process.
  • the ceramic precursor can be cured above 200 °C (to 600 °C).
  • the insulating layer 120 can be coated with an electron transport material precursor to form a second transport layer 130.
  • the second transport layer 130 can be formed using an electron transport material such as indium tin oxide (ITO), aluminum doped zinc oxide (ZnO:Al), indium doped zinc oxide (ZnOTn), and the like.
  • the electron transport material can be deposited from a precursor, for example, but not limited to, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 144.
  • a precursor for example, but not limited to, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 144.
  • organometallic precursors and surfactants e.g., sol-gel
  • solvents e.g.,
  • a passivation layer can be formed between the insulating layer 120 and the first transport layer 110 and/or the second transport layer 130.
  • the passivation layer can include a Cl dope. The Cl can be annealed and the Cl passivation layer can function at the interface between the insulating layer 120 and the first transport layer 110 and/or the second transport layer 130.
  • the second transport layer 130 can be coated with a TCO precursor to form the second conducting layer 140.
  • the TCO precursor can be cured at 200 °C to 600 °C.
  • the high temperature cure at steps 202, 204, and 206 are optional 250 depending on device fabrication requirements. If curing is not performed at steps 202, 204, and 206, a final high temperature cure of 200 °C to 600 °C can be performed after application of the TCO precursor.
  • cascade coating layers 110-140 without a high temperature cure can be preferred to reduce the total number of cures. If a high temperature cure is not performed at each step, a low temperature cure, less than 50° C, can be used to dry each layer between steps.
  • bus bars 142 can be printed or deposited at step 210.
  • the device can be coated with a PVSK solution using a technique such as blade coating, slot die coating, capillarity coating, dip coating, drop casting, spin coating, or similar method.
  • the PVSK solution infiltrates the porous layers of the device.
  • the passivation of the conducting layer can be achieved by heating in the presence of O2, H2, or an inert gas.
  • the passivation of the device is achieved by chemical treatment.
  • the PVSK surface passivation can be achieved at the interface with the layer by substituting some of the“A-type” cation with a cation linked to a coordinating or chelating group that interacts with the layer structure.
  • passivation is achieved by adding excess Pbl to the PVSK solution with the intent of the Pbl phase separating out at the interface between the layer and the PVSK. Passivation is done to reduce charge recombination otherwise increased due to the surface area added by the scaffold.
  • a PVSK crystal structure is formed by curing the device at a temperature between 80 °C and 150 °C.
  • PVSK crystals melt at approximately 150 °C. The melted PVSK crystals can be deposited on the surface of the device and infiltrate the pores in each layer of the device.
  • Embodiments of the present invention perform high temperature cure processes for layers 110-140, i.e., curing at temperatures greater than 200 °C, before the PVSK is infiltrated into the porous layers, including layers 110-140. Accordingly, these high temperature cure processes, which would otherwise adversely impact crystallized PVSK, are performed before the PVSK is infiltrated into the porous layers and then crystallized at a temperature less than 180 °C. In some embodiments it is preferable to cure the PVSK solution at a temperature closer to, or less than, 100 °C. As a result, embodiments of the present invention are able to fabricate high quality versions of layers 110-140 while concurrently forming high quality layers of PVSK.
  • FIG. 2 provides a particular method of fabricating a perovskite based PVC according to an embodiment of the present invention. Other sequences of steps may also be performed according to alternative embodiments. Moreover, the individual steps illustrated in FIG. 2 may include multiple sub steps that may be performed in various sequences as appropriate to the individual step.
  • FIG. 3 A illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in a p-i-n superstrate configuration according to an embodiment of the present invention.
  • the PVC 300 is fabricated in a superstrate configuration having p-i-n construction.
  • the device 300 is a PVC comprising a glass superstrate 302, a first conducting layer 310, a first transport layer 320, an insulating layer 330, a second transport layer 340, and a second conducting layer 350.
  • the glass superstrate 302 is configured to receive light, and may be formed of a transparent material such as a rigid or flexible glass.
  • the glass superstrate 302 can be coupled to a first conducting layer 310.
  • additional layers can be formed between one or more layers such as a passivation layer, a capping layer, a barrier layer, and the like.
  • one or more of the layers in device 300 can be porous to form a scaffold structure that can be infiltrated with a PVSK solution to form a PVSK crystal structure.
  • a precursor solution can be used to create a given layer using particle dispersion.
  • the particles in each layer should not be smaller than the pores of the underlying layer.
  • the insulating layer 330 can include large pores in order to fit a large volume of absorber material such as the PVSK solution.
  • the second transport layer 340 can be comprised of larger particles than the pore openings of the insulating layer 330.
  • the insulating layer 330 can be created using surfactants solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, that are not cured out of the device 300 until after one or more layers are coated on the device 300 as required.
  • the first conducting layer 310 can be an electrode for device 300.
  • the first conducting layer 310 can be a transparent conducting oxide (TCO) to allow light to pass into the underlying layers and may be formed of indium tin oxide (“ITO”), zinc oxide, indium zinc oxide, fluorine doped tin oxide, or another transparent conductive material.
  • the first conducting layer 310 can be in electrical contact with a first transport layer 320.
  • the first conducting layer 310 is a dense material with a zero percent or near zero percent porosity.
  • an optional thin film such as a passivating layer can be deposited on the first conducting layer 310.
  • These conducting layers and thin film layers can be deposited using atomic layer deposition (ALD), Chemical vapor deposition (CVD), chemical solution deposition (CSD), and the like.
  • the first transport layer 320 can be formed using a hole transport material.
  • the first transport layer 320 can include a tunnel barrier.
  • the hole transport material can be a p-type semiconductor configured to facilitate the movement of positive charge, i.e., "holes," in the first transport layer 320.
  • the first transport layer 320 can be fabricated using nickel oxide (NiOx), barium nickel oxide (BaNiOx) and/or another hole transport material.
  • the first transport layer 320 is a dense layer of minimal or zero percent porosity. In these embodiments, the thickness can be between 0.001 pm and 1.0 pm, in preferred embodiments, the thickness can be between 0.001 pm and 0.2 pm.
  • the first transport layer 320 can comprise two or more sub- layers.
  • the first sub-layer can be a dense layer of hole transport material coupled to the first conducting layer 310.
  • the second sub-layer on top of the first sub-layer can be a porous layer of hole transport material.
  • the porosity of the second sub-layer can vary from zero to 30 % porous.
  • the porous sub-layer layer facilitates contact between the PVSK crystal formed at the bottom of the insulating layer 330 and first transport layer 320.
  • the thickness can be between 0.001 pm and 1.0 pm, in preferred embodiments, the thickness can be between 0.001 pm and 0.10 pm.
  • the first transport layer 320 can be in electrical contact with the insulating layer 330.
  • the insulating layer 330 can be an insulating ceramic.
  • Insulating ceramics include transition metal oxides such as alumina (AI2O3), zirconia (ZrCfe), titania (T1O2), and the like.
  • the insulating layer 330 can be porous to facilitate the infiltration of a PVSK solution into the porous insulating layer 330 and any porous layers coupled to the insulating layer such as a second porous sub-layer of the first transport layer 320 or to make contact with a dense first transport layer 320.
  • the porosity can vary from 10 to 90 % porous; in preferred embodiments, between 70 and 90 %. It will be appreciated that approximately 90 % porosity can be the limit of structural stability for some porous oxides.
  • the thickness for the insulating layer 330 can be 0.25 pm to 10 pm.
  • the preferred thickness for the insulating layer can vary from 0.5 pm to 5.0 pm and 1.0 pm to 3.0 pm depending on the absorbance of the PVSK crystal, the porosity of the insulating layer, and the degree to which recombination has been mitigated with passivation.
  • the second transport layer 340 can be formed on the insulating layer 330.
  • the second transport layer can be formed using an electron transport material.
  • the electron transport material can be an n-type semiconductor configured to facilitate the movement of electrons in the second transport layer 340.
  • the second transport layer 340 can be fabricated using titanium oxide (TiOx), tin oxide (SnOx) and/or another electron transport material.
  • the second transport layer 340 can be fabricated to be a porous layer.
  • the porosity can vary from 0 to 40 % porous. In some preferred embodiments, the porosity can vary between five and 10 %.
  • a porous second transport layer can be fabricated using, for example, but not limited to, a nanoparticle dispersion system, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and the like.
  • organometallic precursors and surfactants e.g., sol-gel
  • solvents, binders, dispersants, or other materials for example, but not limited to, polymer beads, and the like.
  • surfactants, solvents, binders, dispersants, or other materials for example, but not limited to, polymer beads, can be evaporated during the curing process leaving a porous material.
  • a porous second transport layer 340 facilitates the infiltration of a PVSK solution into the porous insulating layer 330, the first transport layer 320, and the first conducting layer 310.
  • the thickness for the second transport layer 340 can be between 0.02 pm to 1.0 pm. In some embodiments the preferred thickness is as thin as possible, or 0.02 pm, to reduce the resistance and recombination associated with the second transport layer 340.
  • the second transport layer 340 can be thick enough to keep the filled PVSK crystal structure from touching the second conducting layer 350 when a capping layer (discussed above) is used in device 300. In some embodiments, the second transport layer 340 can be in electrical contact with the second conducting layer 350.
  • the second conducting layer 350 can be a second TCO or a carbon material.
  • the second conducting layer 350 can be an electrode for device 300.
  • the second conducting layer 350 can be formed by, for example, sputtering, ALD, or solution coating.
  • the second conducting layer 350 can be a porous TCO.
  • Transparent conducting oxides can include indium tin oxide (ITO), aluminum doped zinc oxide (ZnO:Al), indium doped zinc oxide (ZnOTn), and the like.
  • the second conducting layer 350 can be made porous using techniques, for example, but not limited to, dispersed nanoparticle precursors, solutions containing organometallic precursors and surfactants, solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, a surfactant templated metal oxide film system using a solution containing
  • organometallic precursors and surfactants e.g., sol-gel
  • solvents, binders, dispersants, or other materials for example, but not limited to, polymer beads, and the like.
  • nanoparticles can sinter together leaving a void or pore.
  • Surfactants, solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, can be evaporated during the curing process leaving a porous material.
  • the porosity of the second conducting layer 350 can vary from 0 to 40 % porous. In some preferred embodiments, the second conducting layer 350 can be as dense as possible while still being permeable to a PVSK solution, for example, the porosity can vary between five and 10 %.
  • 36% porosity represents random close packing of spheres in the second conducting layer 350.
  • the thickness for the second conducting layer 350 can be between 0.02 pm to 5.0 pm. In some preferred embodiments, the thickness can be approximately 0.40 pm.
  • a porous second conducting layer 350 facilitates the infiltration of a PVSK solution into the second transport layer 340, the porous insulating layer 330, and the first transport layer 320.
  • a carbon-based second conducting layer 350 can be formed on the second transport layer 340.
  • the carbon layer is printable and can be formed on the second transport layer 340 by, for example, a carbon black/graphite conducting layer with a thickness of about 10 pm.
  • the carbon black/graphite conducting layer can be formed by printing a carbon black/graphite composite slurry and sintering at a temperature of approximately 400 °C.
  • a dense second conducting layer 350 can be printed as a dense grid of TCO precursor to fabricate a dense TCO in most of the second conducting layer 350.
  • the grid can be formed with "doors" for the PVSK solution to infiltrate the transport layers and insulating layers.
  • a porosity of 5% to 10% can be achieved.
  • one or more bus bars 352 can be formed on the second conducting layer 350.
  • the one or more bus bars 352 can be formed using lithography, screen printing, flexographic printing, and the like.
  • the bus bars 352 can be cured at high temperatures before the PVSK crystal is formed on the device 300. High temperature deposition can be used to fabricate cheaper, higher quality bus bars formed of aluminum, copper, gold, silver, stainless steel, and the like.
  • porosity is not required if the grid is printed to facilitate the spreading of the PVSK solution underneath the grid lines.
  • the bus bars 352 can be printed at lower temperatures using materials such nickel paste, silver paste, and the like.
  • the one or more bus bars 352 can be a wire mesh.
  • the wire mesh can be inserted between a laminating sheet and the second conducting layer 350.
  • the laminating sheet can be placed on top of device 300 to electrically isolate the device.
  • the grid and laminating sheet can be held in place with, for example, a potting resin.
  • a PVSK crystal structure 354 is indicated by the plurality of points illustrated in FIG. 3A.
  • the PVSK crystal structure 354 can be formed in the pores of device 300 by infiltrating one or more liquid solutions into the porous layers of device 300 using a method such as blade coating, slot die coating, capillarity coating, dip coating, drop casting, spin coating, and the like.
  • the liquid solution can be a PVSK solution or a PVSK melt. Once the solution has infiltrated the pores, device 300 can be cured at a low temperature to form the PVSK crystal structure.
  • porous layers facilitate the fabrication of a PVSK crystal structure 354 in the TCO, second conducting layer 350; the electron transport material, second transport layer 340; the insulating ceramic, insulating layer 330; and the porous sub- layer of the hole transport material, first transport layer 320.
  • a capping layer can be formed on the PVSK crystal structure 354.
  • the capping layer can use a solution, e.g., a capping material, to form a dense one or more dense layers in or above the second transport layer 340.
  • these layers can still require a high temperature to obtain the ideal properties, however because the PVSK is below the capping layer and inside device 300, the heat would not decompose the PVSK.
  • the melting and recrystallization of the PVSK crystal structure 354 below the capping layer can be beneficial.
  • the layers below the intended capping layers must be free of volatile components.
  • the device 300 can be heated to high temperature prior to application of the PVSK and capping layers in order to remove all volatile components.
  • a resin can be coated onto the first transport layer after the pores of the device 300 have been infiltrated with the PVSK solution or the PVSK melt.
  • the PVSK solution or the PVSK melt is not filled to the top of the device 300, for example, to a predetermined amount of about 10 % from the top can be left unfilled.
  • a resin can be used to fill the top 10 % of the porous structure. The resin can be mechanically abraded back to re-expose the second transport layer 340.
  • a dense second conducting layer 350 comprising TCO, nanowire networks, carbon, or the like can be allied on top.
  • FIG. 3B illustrates a simplified cross section of a PVC fabricated using a scaffold structure and an infiltrated PVSK material in an n-i-p superstrate configuration according to an embodiment of the present invention.
  • the PVC 390 is fabricated in a superstrate configuration having n-i-p construction.
  • the device 390 illustrates a different structure from device 300 in FIG. 3 A because the electron and hole transport layers are in a different configuration.
  • Device 360 comprises a glass superstrate 302, a first conducting layer 310, an electron transport layer 360, a porous insulating layer 370, a porous hole transport layer 380, and a porous second conducting layer 350.
  • the layers can be formed using materials and methods discussed in relation to FIG. 3 A.
  • additional layers can be formed between one or more layers such as one or more passivation layers, a capping layer, a barrier layer, and the like.
  • the PVSK crystal structure 354 can be in contact with bus bars 352.
  • some bus bar 352 materials such as silver, can diffuse into PVSK when the temperature reaches to 70 °C.
  • a barrier layer between the porous layers and the electrode can be used to impede diffusion.
  • the barrier layer can be approximately 10 nm.
  • a barrier layer which has an oxygen deficiency property such as MoOx can be used.
  • a dense barrier layer between the second conducting layer 350 and the second transport layer 340 can block infiltration.
  • a capping layer can be used to form a dense layer on the upper layers and performs the functions of the capping layer and the barrier layer.
  • FIG. 4 illustrates a process flow for fabricating the scaffold structure and the infiltrated PVSK material in an superstrate configuration according to an embodiment of the present invention.
  • the process flow illustrated in FIG. 4 can be used to fabricate devices as illustrated in FIG. 3 A.
  • the process 400 begins by providing a substrate, in some embodiments a glass superstrate 302, with a first conducting layer 310.
  • the first conducting layer 310 can be coated with a hole transport material precursor to form the first transport layer 320.
  • the first transport layer 320 can be fabricated to be a porous material.
  • the hole transport material can be deposited using, for example, but not limited to, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 354.
  • organometallic precursors and surfactants e.g., sol-gel
  • solvents e.g., binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 354.
  • the curing temperatures for these oxides generally range from 300 °C to 600 °C and are relatively high in comparison to the melting or crystallization temperature of PVSK.
  • the first transport layer 320 can be coated with a ceramic precursor that can be cured to form the insulating layer 330.
  • the ceramic precursor can be applied using a technique such as blade coating, slot die coating, capillarity coating, dip coating, drop casting, spin coating, or other deposition process.
  • the ceramic precursor can be cured above 200 °C (to 600 °C).
  • the insulating layer 120 can be coated with an electron transport material precursor to form a second transport layer 340.
  • the second transport layer 340 can be formed using an electron transport material such as indium tin oxide (ITO), aluminum doped zinc oxide (ZnO:Al), indium doped zinc oxide (ZnOTn), and the like.
  • the electron transport material can be deposited from a precursor, for example, but not limited to, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 354.
  • a precursor for example, but not limited to, a surfactant templated metal oxide film system using a solution containing organometallic precursors and surfactants (e.g., sol-gel), solvents, binders, dispersants, or other materials, for example, but not limited to, polymer beads, and annealed above 200 °C to ensure high material quality, thereby maximizing compatibility with PVSK crystal structure 354.
  • organometallic precursors and surfactants e.g., sol-gel
  • solvents e.g., binders
  • a passivation layer can be formed between the insulating layer 330 and the first transport layer 320 and/or the second transport layer 340.
  • the passivation layer can include a Cl dope. The Cl can be annealed and the Cl passivation layer can function at the interface between the insulating layer 330 and the first transport layer 320 and/or the second transport layer 340.
  • the second transport layer 340 can be coated with a TCO precursor to form the second conducting layer 350.
  • the TCO precursor can be cured above 200 °C (to 600 °C).
  • the high temperature cure at steps 402, 404, and 406 are optional 450 depending on device fabrication requirements. If curing is not performed at steps 402, 404, and 406, a final high temperature cure of 200 °C to 600 °C can be performed after application of the TCO precursor.
  • cascade coating layers 310-350 without a high temperature cure at each step can be preferred to reduce the total number of cures. If a high temperature cure is not performed at each step, a low temperature cure, less than 50 °C, can be used to dry each layer between steps.
  • a carbon layer can be fabricated as the second conducting layer. The carbon layer can be formed after the high temperature cure of layers 310-340.
  • bus bars 352 can be printed or deposited at step 410. Temperature associated with forming the bus bars 352 can range from 200 °C to 600 °C.
  • the device can be coated with a PVSK solution using technique such as blade coating, slot die coating, capillarity coating, dip coating, drop casting, spin coating, or similar method. Following coating with a PVSK solution, the PVSK solution can infiltrate the porous layers of the device. Following coating with a PVSK solution, the PVSK solution infiltrates the porous layers of the device. In some embodiments, either the layer surface is passivated or the PVSK surface is passivated.
  • the passivation of the conducting layer can be achieved by heating in the presence of O2, Fh, or an inert gas.
  • the passivation of the device is achieved by chemical treatment.
  • the PVSK surface passivation can be achieved at the interface with the layer by substituting some of the“A-type” cation with a cation linked to a coordinating or chelating group that interacts with the layer structure.
  • passivation is achieved by adding excess Pbl to the PVSK solution with the intent of the Pbl phase separating out at the interface between the layer and the PVSK. Passivation is done to reduce charge recombination otherwise increased due to the surface area added by the scaffold.
  • a PVSK crystal structure is formed by curing the device at a temperature between 80 °C and 150 C.
  • PVSK crystals melt at approximately 150 °C. The melted PVSK crystals can be deposited on the surface of the device and infiltrate the pores in each layer of the device.
  • a PVSK crystal structure is formed by curing the device at a temperature between 80 °C and 150 C.
  • Embodiments of the present invention perform high temperature cure processes for layers 310-350, i.e., curing at temperatures greater than 200 °C, before the PVSK is infiltrated into the porous layers, including layers 320-350. Accordingly, these high temperature cure processes, which would otherwise adversely impact crystallized PVSK, are performed before the PVSK is infiltrated into the porous layers and then crystallized at a temperature less than 180 °C. In some embodiments it is preferable to cure the PVSK solution at a temperature closer to, or less than, 100 °C. As a result, embodiments of the present invention are able to fabricate high quality versions of layers 310-350 while concurrently forming high quality layers of PVSK.
  • FIG. 4 provides a particular method of fabricating a perovskite based PVC according to an embodiment of the present invention. Other sequences of steps may also be performed according to alternative embodiments. Moreover, the individual steps illustrated in FIG. 4 may include multiple sub- steps that may be performed in various sequences as appropriate to the individual step.
  • FIG. 5 is a simplified band diagram showing the bandgaps for a semiconductor device according to an embodiment of the present invention.
  • the structure is similar to the embodiments illustrating porous first transport layer, a porous insulating layer, and a porous second transport layer.
  • the hypothetical band diagram 500 includes an electron transport layer 506 (Sn02), a PVSK layer 508 (CsFAMAPb(Ii- x Br x )3), and a hole transport layer 510 (NiOx).
  • the PVSK layer will have a conduction band, E c , at 3.8 eV and a valence band, E v , at 5.4 eV.
  • the bandgap 512 corresponds to the difference between the energies of the conduction and valence bands and will vary accordingly.
  • Conduction and valence bands of adjacent materials are also shown, including the conduction bands of Sn02 (4.0 eV) and NiO (3.0 eV) and the valence bands of Sn02 (5.9 eV) and NiOx (5.1 eV).
  • the porous structure facilitates the formation of high quality transport layers in electrical contact with the PVSK crystal structure and enhances light absorption and conversion efficiency.
  • FIG. 6A illustrates a simplified cross section of a PVC 600 with a TCO layer formed on a porous transport layer according to an embodiment of the present invention.
  • the PVC 600 may include a glass substrate 640, a first transport layer including a dense transport sub-layer 630, for example a dense ETM layer, and a porous transport sub-layer 620, for example a porous ETM layer, a porous insulating layer 610, for example a porous ceramic layer, a second porous transport layer 602, for example a porous HTM layer, a porous TCO layer 650, and a bus bar 606.
  • TCO layer 650 can be formed on a porous hole transport material 602 using sputtering, ALD, and the like.
  • the deposited TCO layer 650 is continuous enough, as illustrated in FIG. 6B, to offer conductivity but leaves sufficient gaps 602 in pores 604 on the surface 608 of the hole transport material 602.
  • FIG. 6B illustrates a plan view of a PVC with a porous TCO layer according to an embodiment of the present invention.
  • FIG 6B shows the location of the cross section, A, illustrated in FIG. 6A.
  • the bus bar 606 shows how the TCO deposited at the surface of the hole transport material 602 provides a surface for a continuous electrical contact.
  • bus bar 606 can be 100 microns wide. In embodiments with a plurality of bus bars the spacing can be at least 1 cm.
  • FIG. 7 illustrates a simplified process 700 for fabricated a perovskite based photovoltaic cell (PVC) with a high temperature electron transport layer (ETL) and a high temperature hole transport layer (HTL) in a scaffold structure.
  • PVC perovskite based photovoltaic cell
  • ETL electron transport layer
  • HTL high temperature hole transport layer
  • the first conducting layer can be a flexible metal foil that facilitates integration of both a high temperature ETL and HTL into a single PVC.
  • the first transport layer can be an ETL or HTL.
  • the first transport layer can be porous.
  • step 714 form a porous insulating layer in electrical contact with the first transport layer.
  • step 716 form a second transport layer.
  • the second transport layer can be porous.
  • the second transport layer may include a dense second transport sub-layer.
  • the second transport layer can be an opposite type of layer as the first transport layer.
  • the first transport layer is a high temperature ETL
  • the second transport layer can be a high temperature HTL.
  • step 718 form a second conducting layer in electrical contact with the porous second transport layer.
  • the second conducting layer can be a porous layer.
  • step 720 perform a curing process at a temperature greater than 200 °C.
  • the high temperature curing process is incompatible with a PVSK layer.
  • a top electrode may be formed on the second conducting layer.
  • step 722 after the high temperature curing process, form a perovskite crystal structure in the porous layers of the photovoltaic cell.
  • a capping layer may be formed on the PVSK crystal structure.
  • the capping layer may be formed by infiltrating a suspension (e.g., sol-gel) or solution of particles, for example, but not limited to, AI2O3 nanoparticles, zirconium(II) oxide (ZrO) nanoparticles, or nanoparticles of another nonconductive oxide, into the spaces of the porous second conducting layer and the dense second transport sub-layer.
  • a suspension e.g., sol-gel
  • particles for example, but not limited to, AI2O3 nanoparticles, zirconium(II) oxide (ZrO) nanoparticles, or nanoparticles of another nonconductive oxide
  • conductive oxide nanoparticles for example, but not limited to, ITO, indium gallium zinc oxide (IGZO), IZO, aluminum doped zinc oxide (AZO), or nanoparticles of another transparent conductive oxide, may be used as a material to form the capping layer.
  • the capping layer material may be a polymer, for example, but not limited to thermoplastic and thermoset polymers for example, but not limited to, poly(methyl methacrylate) (PMMA), epoxy, silicone, urethanes, or other polymer that are transparent at least in the absorption range of the PVSK absorber.
  • an encapsulating layer may be formed over the top electrode to electrically isolate the device.
  • the encapsulating layer may be a polymer, for example, but not limited to, ethylene-co-vinyl acetate (EVA), polyolefin elastomer-based (POE) materials, or other similar materials.
  • FIG. 7 provides a particular method of fabricating a perovskite based PVC according to an embodiment of the present invention. Other sequences of steps may also be performed according to alternative embodiments. Moreover, the individual steps illustrated in FIG. 7 may include multiple sub- steps that may be performed in various sequences as appropriate to the individual step.
  • Electron transport layers, hole transport layers, transparent conductor layers, insulating layers, and PVSK layers may be formed in different combinations and with n-type or p-type dopants, as determined by the requirements of a specific application.
  • Example embodiments have been described with respect to formation of a single photovoltaic cell (PVC) or semiconductor device. The embodiments can be extended to include formation of multiple PVCs or semiconductor devices. For example, multiple instances of a PVC could be formed and connected in series by patterning the electrodes on both sides, and forming alternating electron and hole transport layers separated by an insulating layer.

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Abstract

Cette invention concerne une cellule photovoltaïque, comprenant une première couche conductrice, une première couche de transport en contact électrique avec la première couche conductrice, et une couche isolante poreuse en contact électrique avec la première couche de transport. La cellule photovoltaïque comprend également une seconde couche de transport poreuse en contact électrique avec la couche isolante poreuse, une seconde couche conductrice en contact électrique avec la seconde couche de transport poreuse, et une structure cristalline de pérovskite disposée dans une ou plusieurs de la couche isolante poreuse, de la seconde couche de transport poreuse et de la seconde couche conductrice.
PCT/US2018/062088 2017-11-20 2018-11-20 Procédé et système pour cellule solaire à pérovskites avec structure en échafaudage WO2019100070A1 (fr)

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