WO2019074616A2 - Fabrication de structures en pérovskite empilées - Google Patents

Fabrication de structures en pérovskite empilées Download PDF

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Publication number
WO2019074616A2
WO2019074616A2 PCT/US2018/051245 US2018051245W WO2019074616A2 WO 2019074616 A2 WO2019074616 A2 WO 2019074616A2 US 2018051245 W US2018051245 W US 2018051245W WO 2019074616 A2 WO2019074616 A2 WO 2019074616A2
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pvsk
layer
component
fusing
layers
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PCT/US2018/051245
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WO2019074616A3 (fr
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Alex GOVAERTS
Matthew Robinson
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Energy Everywhere, Inc.
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Priority to EP18866448.6A priority Critical patent/EP3682489A4/fr
Publication of WO2019074616A2 publication Critical patent/WO2019074616A2/fr
Publication of WO2019074616A3 publication Critical patent/WO2019074616A3/fr

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    • 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
    • H10K71/50—Forming devices by joining two substrates together, e.g. lamination techniques
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • 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
  • a layer of perovskite that acts as a solar absorber.
  • PVSK dramatically increases solar conversion efficiency compared to conventional silicon solar cells.
  • PVSK encompasses a number of different materials, each having the same type of crystal structure as calcium titanium oxide (CaTi0 3 ). Examples include perovskites formed using methylammonium halides, which have a formula of CFLNFLX, where X is bromine, chlorine or iodine, e.g., a perovskite having the formula CH3NH3PBX3.
  • PVSK can be formed on semiconductor materials using various techniques. The process is monolithic and generally begins by coating a layer of material onto a semiconductor substrate, then adding successive layers including a PVSK layer.
  • PVSK is a relatively fragile material, being brittle, water soluble and heat sensitive. This has limited the choice 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. PVSK has uses beyond solar cells; research is currently being conducted into PVSK as a component of lasers and light emitting diodes. BRIEF SUMMARY OF THE INVENTION
  • the present disclosure relates generally to fabrication of semiconductor devices that include a PVSK layer. More particularly, embodiments of the present disclosure relate to formation of a solar cell by joining two portions of the cell, each portion having a PVSK layer, and then fusing the PVSK layers together to form a single PVSK layer.
  • Embodiments of the present disclosure relate to fused PVSK layers produced through stoichiometric variation.
  • additional material is introduced before the PVSK layers are fused.
  • This additional material can be introduced in various ways, including incorporating the additional material as additives when forming one or more PVSK layers or introducing the additional material after the PVSK layers have been formed.
  • additional materials may include PVSK components, such as precursors, or other materials suitable for use in recrystallizing the PVSK layers (e.g., solvents).
  • Precursors are compounds that chemically react to form another compound (e.g., a PVSK compound).
  • a PVSK component may comprise one or more precursors and/or one or more chemical elements that chemically react to form PVSK.
  • the chemical reaction can occur spontaneously when the PVSK components are combined, or in response to a stimulus such as heat, light, and/or pressure.
  • the additional material may form new PVSK, i.e., an additional quantity of PVSK not present prior to fusing.
  • the additional material is absorbed into the original PVSK layers, as excess material or to form new PVSK by making up for a missing component in the original PVSK layers.
  • stoichiometric variation is performed when forming the original PVSK layers, so that one PVSK layer has a different component stoichiometry than another PVSK layer.
  • the bandgap is similar to graded heterojunctions formed at the interface between two semiconductor materials with different bandgap energies, and may be formed to facilitate or inhibit particle mobility depending on the direction of bandgap change and the bandgaps of adjacent layers.
  • FIG. 1 is a simplified side view diagram illustrating layers in a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 2 is a flowchart illustrating a method of forming a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 3 is a hypothetical band diagram showing a graded bandgap for a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 4 is a hypothetical band diagram showing a graded bandgap for a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 5 is a flowchart illustrating a method of fusing PVSK layers according to an embodiment of the present disclosure.
  • FIG. 6 is a simplified side view diagram illustrating layers in a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 7 is a simplified side view diagram illustrating layers in a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 8 shows a roller configuration for forming a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 9 shows a roller configuration for forming a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 10 shows a roller configuration for forming a semiconductor device according to an embodiment of the present disclosure.
  • FIG. 11 shows a roller configuration for forming a semiconductor device according to an embodiment of the present disclosure.
  • the present disclosure relates generally to techniques for fabrication of semiconductor devices that include a PVSK layer. More particularly, embodiments of the present disclosure involve methods and systems for forming a semiconductor device by fusing two pieces of the device together, each piece containing its own PVSK layer, to form a fused PVSK layer.
  • Example embodiments are described with respect to formation of a solar cell. However one of skill in the art will understand that the embodiments can readily by adapted to formation of other types of semiconductor devices.
  • FIG. 1 is a simplified side view diagram illustrating layers in a semiconductor device 100 according to an embodiment of the present disclosure.
  • the device 100 is a solar cell comprising a first portion 102 and a second portion 104.
  • the first portion 102 includes a front substrate 110, a transparent electrode 120, an electron transport layer 130 and a PVSK layer 140.
  • the second portion 104 includes a PVSK layer 150, a hole transport layer 160, a conductive diffusion barrier 170 and a back substrate 180.
  • the front substrate 110 is configured to receive light, and may be formed of glass or a transparent plastic such as polyethylene terephthalate (“PET").
  • PET polyethylene terephthalate
  • the electrode 120 is also transparent to allow light to pass into the underlying layers and may be formed of indium tin oxide ("ITO"), which can be deposited by sputtering.
  • ITO indium tin oxide
  • the electron transport layer 130 may be formed of tin oxide (Sn0 2 ).
  • Sn0 2 can be deposited at a temperature above the melting temperature of PVSK, e.g., the first PVSK layer 140.
  • PVSK layers 140 and 150 may, but need not, have the same composition.
  • layers 140 and 150 may be formed of the same perovskite, but with different materials added.
  • layers 140 and 150 may be two different perovskites.
  • the layers 140, 150 may be spin-coated.
  • Other techniques that form PVSK layers are also suitable for use with the example embodiments described herein.
  • the layers 140 and 150 are joined together and fused using techniques described below, thereby forming a laminated structure comprising a fused PVSK layer.
  • Hole transport layer 160 may be formed of nickel oxide (NiOx) deposited using, for example, a sol gel technique and annealed above 300° C to ensure high material quality, thereby maximizing compatibility with PVSK layer 150. This annealing temperature is relatively high in comparison to the melting temperature of PVSK, e.g., the second PVSK layer 150.
  • Diffusion barrier 170 may be formed of titanium nitride (TiN) and may not be required, for example, if the hole transport layer 160 is a sufficient diffusion barrier by itself.
  • Back substrate 180 may be formed of aluminum (Al) or another metal such as silver (Ag). In one embodiment, substrate 180 is an aluminum foil with an insulating layer on its uncoated side to electrically isolate the substrate 180 from the external environment and/or to facilitate spin- coating processes by providing a degree of rigidity to the substrate 180.
  • FIG. 2 is a flowchart illustrating a method 200 of forming a semiconductor device according to an embodiment of the present disclosure.
  • the method 200 can be used to form the solar cell of FIG. 1, but is readily adaptable for forming other types of semiconductor devices.
  • a transparent electrode is formed on a front substrate, for example, by depositing a layer of ITO to form electrode 120 on substrate 110.
  • an electron transport layer (e.g., layer 130) is formed using an appropriate material such as SnCh.
  • the technique by which the electron transport material is formed may vary depending on the material of the front substrate, for example, a high temperature process for a glass substrate or a lower temperature process for a PET substrate, as mentioned earlier.
  • a first PVSK layer (e.g., layer 140) is formed on the electron transport layer, for example, using a spin-coating process. This completes the first portion of the solar cell.
  • step 216 formation of the second portion of the solar cell begins with adding a diffusion barrier material such as TiN to a back substrate (e.g., substrate 180), thereby forming a diffusion barrier (e.g., diffusion barrier 170).
  • a diffusion barrier material such as TiN
  • a back substrate e.g., substrate 180
  • a diffusion barrier e.g., diffusion barrier 170
  • the back substrate can be an opaque conductor such as aluminum.
  • a hole transport layer e.g., layer 160 is formed on the diffusion barrier using, for example, NiOx.
  • a second PVSK layer (e.g., layer 150) is formed on the hole transport layer, for example, using the same PVSK and process as in step 214.
  • the two portions of the cell are joined by stacking them together with the PVSK layers facing each other (either in direct contact as shown in FIG. 1 or with some additional material in between the PVSK layers as shown in FIG. 6), then fusing the PVSK layers to form a single PVSK layer.
  • the two portions may be stacked one on top of the other.
  • the two portions may also be stacked side-by-side.
  • Various techniques for fusing two PVSK layers together will be described further below.
  • the PVSK layers are chemically and/or physically fused at an interface between the PVSK layers.
  • an appropriate amount of heat and pressure may be applied to the layers 140 and 150 (and to any intervening material between the PVSK layers) to cause the layers 140 and 150 to recrystallize. That is, the crystalline structure of the layers 140, 150 may begin to break down in response to application of heat and pressure (possibly with the aid of additional materials described below) and then reorganize into a crystalline structure (e.g., after reducing the temperature and/or pressure).
  • the interface between the PVSK layers refers to the surfaces where the two portions meet when stacked and may comprise a surface of one or more PVSK layers and/or a surface of one or more additional layers interposed between the PVSK layers (e.g., a layer comprising a PVSK component, as shown in FIG. 6).
  • Heat, pressure, and/or other stimuli can be applied to the stacked portions as a whole, i.e., the entire device.
  • pressure can be applied to the stacked portions using a flat press or rollers and in a heated environment.
  • a stimulus can be applied in a local manner to one or more layers of the stack (e.g., to the PVSK layers and/or the interface between the PVSK layers, but not the rest of the stack).
  • a static press may be sufficient to apply pressure over the entire device area all at once.
  • the two portions can be pressed between two rollers.
  • a PVSK layer is heated to melting and then allowed to cool to a certain homologous temperature (a fraction of its melting temperature)
  • the grains at or near the surface of the PVSK layer will recrystallize.
  • PVSK typically crystallizes at less than 200° C.
  • the addition of pressure while not strictly necessary, may reduce the amount of time needed to recrystallize the PVSK layers, and may also help to maintain the integrity of the PVSK by preventing volatile components of PVSK from vaporizing during heating.
  • each portion having a substrate and a PVSK layer.
  • the portions are then joined by fusing the PVSK layers using heat, pressure, and/or other stimuli.
  • the materials and processes used to form each portion can be the same as those used for conventional PVSK structures.
  • the PVSK layers are the last layers to be added (aside from any additional materials that may be introduced between the PVSK layers during the fusing process)
  • materials and processes that have not previously been considered for use in combination with PVSK are also suitable for use in forming a semiconductor device in accordance with the techniques described herein.
  • materials that are amenable to high temperature processing can be used for the electron and hole transport layers. NiOx and SnCh are examples of such materials.
  • SnCh may be formed using aqueous processing without risk of damaging the water soluble PVSK.
  • the choice of materials is not limited to those that can be coated onto PVSK without degrading it.
  • the back substrate material is not tied to the front substrate material, and the cell no longer has to be formed as a monolithic unit.
  • differing PVSK formulations can be used for the front and back portions.
  • the ratio of halide in one PVSK layer to halide in another PVSK layer may not be 1 : 1. This type of stoichiometric variation permits the formation of a graded bandgap in the fused PVSK layer, as shown in FIG. 3.
  • FIG. 3 is a hypothetical band diagram showing a graded bandgap for a semiconductor device according to an embodiment of the present disclosure.
  • the structure is similar to that previously described with respect to FIG. 1 and includes, from back to front: an Al layer 310, a NiOx layer 320, a first PVSK layer 330 formed of CsF AMAPb(Ii-xBr x ) 3 , a second PVSK layer 340 formed of CsFAMAPbb, an SnC-2 layer 350 and an ITO layer 360.
  • the front side is indicated by a photon 90, which is directed towards the ITO layer 360.
  • the fusing process will cause bromine to diffuse from the first PVSK layer 330 into the second PVSK layer 340.
  • the fused PVSK layer will have a conduction band varying from that of CsFAMAPb(Ii-xBrx) 3 (3.5 eV) to that of CsFAMAPbb (3.8 eV).
  • the valence band of the fused PVSK layer will vary from 5.5 eV to 5.4 eV.
  • the bandgap corresponds to the difference between the energies of the conduction and valence bands and will vary accordingly.
  • Conduction and valence bands of the adjacent layers are also shown, including the conduction bands of Sn0 2 layer 350 (4.2 eV) and ITO layer 360 (4.7 eV) and the valence band of NiOx layer 320 (5.2 eV).
  • the graded bandgap enhances light absorption and conversion efficiency, as electrons liberated from the fused PVSK layer (330, 340) by incoming photons are immediately swept from a higher bandgap portion of the fused layer to a lower bandgap portion of the fused layer, towards the electron transport layer, i.e., towards Sn0 2 layer 350.
  • a graded bandgap can be formed even if the two PVSK layers are allowed to fully diffuse together. That is, the diffusion may reach an equilibrium state in which the resultant structure is non-homogeneous and has a graded bandgap.
  • FIG. 4 is a hypothetical band diagram showing a graded bandgap for a semiconductor device according to another embodiment of the present disclosure.
  • the relative order of the perovskites is reversed compared to the arrangement in FIG. 3. That is, the structure in FIG. 4 comprises, from back to front, an Al layer 410, a NiOx layer 420, a first PVSK layer 430 formed of CsF AMAPbb, a second PVSK layer 440 formed of CsF AMAPb(Ii-xBr x ) 3 , an Sn0 2 layer 450 and an ITO layer 460.
  • the bandgap is graded in the opposite direction so that particle mobility is impeded; electrons would need a greater amount of energy to travel to the Sn0 2 layer 450. From the examples in FIGS. 3 and 4, it is apparent that stoichiometric variations in the PVSK layers can form a graded bandgap region after fusing the layers, and that the bandgap choices will determine the ease with which particles move between the various layers. Accordingly, a graded bandgap PVSK region may have applicability in other semiconductor devices besides solar cells, such as laser devices or light emitting diodes. Graded bandgap PVSK may also form the basis for a solar cell that has no electron or hole transport layers. [0037] FIG.
  • the method 500 begins in step 510, with the application of PVSK components (e.g., precursors) to the interface between two PVSK layers.
  • PVSK components e.g., precursors
  • the PVSK components may operate as reflow materials that lower the temperature required for
  • the reflow materials are analogous to flux agents that are sometimes used when joining metals or glass.
  • suitable reflow materials include any low melting temperature component of a desired PVSK, such as: a methylammonium halide, a bromine deposited from a dilute ether solution, a monolayer of dimethyl sulfoxide (DMSO), and a methylammonium lead bromide (useful for joining an iodide containing PVSK and/or a heavier cation containing PVSK).
  • the reflow material is a PVSK component or precursor that participates in a chemical reaction to form additional PVSK at the interface.
  • the reflow material does not necessarily have to be a precursor or PVSK component, nor does the reflow material necessarily have to participate in recrystallization.
  • the reflow material comprises a solvent that is introduced and then removed from the interface prior to pressing the two portions together.
  • the solvent may at least partially dissolve PVSK in the PVSK layers (e.g., localized dissolving of PVSK located at or near the interface), for example, to prepare the PVSK layers for recrystallization.
  • suitable solvents include Dimethylformamide (DMF) and gamma-Butyrolactone (GBL).
  • Step 510 is illustrated in FIG. 6, which shows an example semiconductor device 600 formed by adding an "A" component 601 onto an existing PVSK layer 640 of a first portion comprising a front substrate 610, a transparent electrode 620, an electron transport layer 630 and the PVSK layer 640.
  • a corresponding "B" component 605 is added onto an existing PVSK layer 650 of a second portion comprising the PVSK layer 650, a hole transport layer 660, a conductive diffusion barrier 670 and a back substrate 680.
  • each of the components 601 and 605 may include one or PVSK precursors that chemically combine to form PVSK having a desired formula.
  • the PVSK to be formed has the formula ABX 3 , where A and B are in a 1 : 1 stoichiometric ratio, and X is an element of A and B.
  • the A component 601 may include the precursor methylammonium bromide (MABr) or the precursor
  • Examples of materials that can participate in a chemical reaction to form PVSK include: a methylammonium halide, a formamidinium halide, a cesium halide, a hydrogen halide, or a lead halide perovskite phase.
  • FIG. 6 shows components added onto both PVSK layers 640, 650.
  • Other embodiments may involve the introduction of only one PVSK component (e.g., a single precursor) at the interface to lower recrystallization temperature, thereby facilitating fusing without forming new PVSK. After recrystallization, any excess remaining quantity of the PVSK component would be incorporated into the fused PVSK layer as intrinsic defects. However, PVSK is fairly tolerant to such defects, which would not significantly impact solar cell performance.
  • PVSK component e.g., a single precursor
  • step 512 the PVSK layers are pressed together and heat or light is applied.
  • PVSK may begin to form through chemical reaction upon contact, even without the application of heat/light or pressure.
  • step 514 heat/light and pressure continue to be applied until a crystallization temperature is reached. This continues for an amount of time sufficient to fully recrystallize or form PVSK at or near the interface.
  • the method 500 may begin in step 516 by forming the PVSK layers with additives in the form of excess components.
  • Step 516 is illustrated in FIG. 7, which shows an example semiconductor device 700 with a first portion comprising a front substrate 710, a transparent electrode 720, an electron transport layer 730 and a PVSK layer 740.
  • a second portion comprises a PVSK layer 750, a hole transport layer 760, a conductive diffusion barrier 770 and a back substrate 780.
  • FIG. 7 shows an example semiconductor device 700 with a first portion comprising a front substrate 710, a transparent electrode 720, an electron transport layer 730 and a PVSK layer 740.
  • a second portion comprises a PVSK layer 750, a hole transport layer 760, a conductive diffusion barrier 770 and a back substrate 780.
  • PVSK layer 750 has excess "A” components 45 and PVSK layer has excess "B” components 55, where A, B and the desired PVSK formula can be the same as discussed above with respect to FIG. 6.
  • the excess A and B components are thus intrinsic to the PVSK layers and may be present in a 1 : 1 ratio so that all of the excess
  • the entire structure may be annealed in an environment containing a vapor form of a PVSK component, e.g., any of the components mentioned earlier with respect to FIG. 5.
  • the environment may be set to an overpressure, that is, greater than atmospheric pressure.
  • This vapor assisted annealing step may help prevent the loss of volatile components that would otherwise evaporate during annealing, since such components are already present in the annealing environment.
  • the vapor may also form a monolayer around the interface, operating as a reflow material to enhance the quality of the bonding of the PVSK layers.
  • rollers As mentioned earlier, two PVSK containing portions can be pressed together using rollers.
  • the following section describes some example roller configurations suitable for forming a semiconductor device in accordance with certain embodiments of the present disclosure.
  • the roller configurations can be used, for example, to implement the embodiments depicted in FIGS. 1 to 7.
  • FIG. 8 shows a roller configuration 800 that permits continuous roll-to-roll processing, in accordance with certain embodiments.
  • the roller configuration 800 supports the application of heat and pressure sufficient to recrystallize PVSK.
  • the roller configuration 800 includes a first roller 810 and a second roller 820.
  • Roller 810 carries a first film 812.
  • Roller 820 carries a second film 822.
  • Each of the films 812, 822 includes at least a PVSK layer and, optionally, additional layers of materials such as the layers shown in FIG. 1.
  • the PVSK layers may form the topmost portions of the films 812, 822.
  • the topmost portions of films 812, 822 may comprise PVSK components (e.g., a precursor layer).
  • the topmost portions of the films 812, 822 are formed as coatings. Additional layers can also be added after fusing the films 812, 822 (e.g., added onto a front or back substrate).
  • the roller configuration 800 permits recrystallization to occur at the nip 830 of the rollers, where the films 812, 822 are pressed together so that the topmost portions contact each other.
  • Film 812 travels in direction 814.
  • Film 822 travels in direction 824.
  • the process parameters can be adjusted for higher heating ramp rates and shorter heating times, as appropriate.
  • roller configuration 800 also allows for additional processes to achieve
  • plasma processing is incorporated into the recrystallization process by applying plasma (represented by arrows 850) at the nip 830.
  • the plasma comprises one more ionized gases (e.g., oxygen, nitrogen, etc.) and can be atmospheric plasma or plasma supplied in a vacuum chamber.
  • the plasma may comprise one or more reactive gases that induce
  • the reactive gas may chemically complete a PVSK formula to form a continuous stacked PVSK film.
  • the reactive gas may interact with PVSK components that participate in a chemical reaction (e.g., the reactive gas may heat and/or volatilize a component to enable the component the combine with another component to form PVSK). Plasma may also participate in
  • the reactive plasma is applied directly to two already formed PVSK layers (rather than precursors) at the nip 830 to induce recrystallization of the PVSK layers into a single fused PVSK layer.
  • one or more gaseous reagents may be supplied at the nip 830 when converting a precursor in one or more of the films (e.g. PbI2 or some mixed halide stoichiometry) into PVSK.
  • a gaseous reagent may comprise a PVSK precursor, a solvent, or an acid.
  • the gaseous reagent may participate in the chemical reaction(s) occurring at the nip 830 (e.g., to complete a PVSK formula). Because the reactions occur at the nip 830, any gaseous byproducts of the reaction(s) will remain in the atmosphere rather than being trapped in the fused PVSK layer.
  • gaseous reagents are supplied at the nip 830 when recrystallizing two already formed PVSK layers into a fused PVSK layer.
  • the gas e.g. methyl ammonium iodide
  • the gas may include a volatile component of the PVSK and may be supplied with an overpressure so that equilibrium in a PVSK thermal decomposition reaction is maintained (i.e., so that thermal decomposition is limited or prevented entirely).
  • a gaseous reagent can be used to prevent PVSK from decomposing (e.g., into one or more precursors) in the presence of heat. This allows for higher heating rates and/or temperatures, which would otherwise cause PVSK decomposition during the fusing process. In this manner, a higher throughput rate can be achieved.
  • FIG. 9 shows a roller configuration 900 in accordance with certain embodiments.
  • light is applied (instead of heat) with pressure to either convert precursors on film 912 and/or film 922 or to recrystallize already formed PVSK into a fused PVSK layer.
  • at least one roller 920 is transparent so that light 950 can travel through the roller to the nip 930.
  • the light 950 can be supplied from light source inside the roller 920.
  • the light 950 may be from a pulsed lamp inside the roller (e.g., a lamp that emits ultraviolet light, visible light, or infrared light) or from a laser source inside the roller.
  • the roller configuration 900 is similar to that used in roll-to-roll nanoimprint lithography.
  • the opposite roller 910 which does not have to be transparent, may be cooled to remove excess heat from the system.
  • the roller configuration 900 also allows for the supply of gaseous reagents at the nip 930 of the rollers, as described in connection with previous embodiments.
  • FIG. 10 shows a roller configuration 1000 in accordance with certain embodiments.
  • the roller configuration 1000 permits continuous roll-to-roll processing and includes multiple rollers connected by a belt.
  • a first roller group 1010 comprises multiple rollers (e.g., three rollers) connected by a belt 1040.
  • a second roller group 1020 comprises multiple rollers connected by a belt 1050.
  • the roller configuration 1000 provides a larger surface area over which the films 1012 and 1022 are in contact, thereby allowing for a longer processing time for applying heat and pressure. Longer processing times may be beneficial if the process parameters cannot be constrained to a shorter processing time required with a configuration having a single pair of rollers.
  • Techniques described in connection with the earlier example roller configurations can also be applied to the roller configuration 1000. For example, plasma or gaseous reagents can be applied at a nip 1030 if desired, and the rollers and belt on one side can be made transparent to allow for light-induced processing.
  • FIG. 11 shows a roller configuration 1100 in accordance with certain embodiments.
  • the roller configuration 1100 includes a roller 1110 and a roller 1120, each roller having flat surfaces.
  • the rollers 1110, 1120 may be hexagonal (as shown in the figure), square, or some other geometric shape with flat surfaces.
  • the roller configuration 1100 permits semi- continuous processing of PVSK structures, e.g., to form a laminated film 1112.
  • the two films which are pressed together by the rollers 1110, 1120 to form the film 1112 are omitted from the figure.
  • the rollers 1110, 1120 can be used to perform the same processes that could be performed using a static flat press in a continuous fashion.
  • one or more PVSK layers may be formed with a deficit of components, i.e., starved.
  • the PVSK layers could, for instance, be formed with less bromine, with the missing quantity of bromine being added at the interface to diffuse into the PVSK layers during the fusing process, thereby chemically completing the PVSK.
  • Another variation is the introduction of elements, such as n-type or p-type dopants, into the fused PVSK layer by applying an overpressure or an interfacial coating that allows the elements to diffuse into, possibly throughout, the fused layer. This may be useful for adding elements that are difficult to incorporate when forming the original, unfused PVSK layers.

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  • Thin Film Transistor (AREA)

Abstract

L'invention concerne des techniques de formation d'un dispositif à semi-conducteur via la fusion d'une première couche de PVSK sur une première portion du dispositif avec une seconde couche de PVSK sur une seconde portion du dispositif. Les portions sont empilées de telle sorte que les couches de PVSK se font face. Les couches de PVSK peuvent être fusionnées en appliquant de la chaleur ou de la lumière, ainsi qu'une pression. La fusion peut comprendre l'ajout d'un solvant ou d'un premier composant PVSK. Le premier composant PVSK peut être un matériau qui abaisse une température de fusion de la PVSK dans les couches de PVSK de sorte à faciliter la recristallisation de la PVSK. Le premier composant PVSK peut être combiné à un second composant PVSK pour former une PVSK supplémentaire. Les composants PVSK peuvent être ajoutés après que les couches de PVSK ont été formées ou des additifs à l'intérieur des couches de PVSK. Les couches de PVSK peuvent également être fusionnées sans ajouter de composants ou de solvants.
PCT/US2018/051245 2017-09-15 2018-09-14 Fabrication de structures en pérovskite empilées WO2019074616A2 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110660925A (zh) * 2019-10-16 2020-01-07 复旦大学 一种卷对卷层压式钙钛矿led及其制备方法
CN111725407A (zh) * 2020-06-18 2020-09-29 青海黄河上游水电开发有限责任公司光伏产业技术分公司 叠层钙钛矿电池的制作方法、叠层钙钛矿电池
EP3996150A4 (fr) * 2019-08-08 2023-08-02 Korea University Research and Business Foundation Élément photoélectrique pérovskite et son procédé de fabrication

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6074962B2 (ja) * 2012-09-13 2017-02-08 日本ゼオン株式会社 ペロブスカイト化合物を用いた光電変換素子およびその製造方法
US20160068990A1 (en) * 2013-04-18 2016-03-10 Drexel University Methods of forming perovskite films
US20160190377A1 (en) * 2013-08-06 2016-06-30 Newsouth Innovations Pty Limited A high efficiency stacked solar cell
WO2016111576A1 (fr) * 2015-01-08 2016-07-14 한국화학연구원 Procédé de production de dispositif comprenant un film de composé pérovskite hybride inorganique/organique et dispositif comprenant un film de composé pérovskite hybride inorganique/organique
KR101707050B1 (ko) * 2015-11-03 2017-02-17 재단법인대구경북과학기술원 페로브스카이트계 광흡수층의 제조방법 및 이에 따라 제조되는 광흡수층을 포함하는 페로브스카이트계 태양전지

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3996150A4 (fr) * 2019-08-08 2023-08-02 Korea University Research and Business Foundation Élément photoélectrique pérovskite et son procédé de fabrication
CN110660925A (zh) * 2019-10-16 2020-01-07 复旦大学 一种卷对卷层压式钙钛矿led及其制备方法
CN111725407A (zh) * 2020-06-18 2020-09-29 青海黄河上游水电开发有限责任公司光伏产业技术分公司 叠层钙钛矿电池的制作方法、叠层钙钛矿电池

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EP3682489A2 (fr) 2020-07-22
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