Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/24—Lead compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/32—Radiation-absorbing paints
• • 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
  • H10K85/30—Coordination compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/20—Light-sensitive devices
  • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• • 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
  • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
• • 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

• the invention relates to organic-inorganic substances with variable composition, serving as an initial reagent for obtaining organic-inorganic perovskites as well as to the methods of obtaining organic-inorganic light-absorbing materials with perovskite structure, being used in perovskite solar cells production.
• the disadvantage of the afore-mentioned precursors is that they require the use of a solvent and special reaction conditions to ensure reaction proceeding to obtain organic-inorganic perovskite because they are solid-state materials and thus complicate technological process, increase production and environmental risks and have a negative impact on the health of employees, involved in organic-inorganic perovskite production process.
• the Objective of the claimed technical solution is the development of simple, quick and low-waste method of obtaining organic-inorganic light-absorbing materials with perovskite structure in a solvent- free way as well as the synthesis of a composition to be used for afore-said methods implementation, which allows obtaining materials suitable for the use in solar cells.
• the technical outcome is the simplification and acceleration of obtaining organic-inorganic light-absorbing materials with perovskite structure, including organic-inorganic perovskites and perovskite-like compounds containing Pb, Sn, Bi, in a solvent-free way, particularly, at room temperature, with capability of the use of the obtained materials in solar cells.
• the material with perovskite structure can be obtained by mixing two reagents AB-nB 2 and D with subsequent elimination of the excessive reagents, where the first reagent is a variable composition AB-nB 2 , where n>l, A stands for methylammonium MA + (CH 3 NH 3 + ), formamidinium, FA + ((NH 2 ) 2 CH + ), guanidinium Gua (C(NH 2 ) 3 + ), cesium Cs + or a mixture thereof, B stands for CI " , Br " , ⁇ or a mixture thereof, whereas Cl 2 , Br 2 , 1 2 or a mixture thereof can be used as component B 2 , while the second reagent D is chosen from elemental Sn, Pb, Bi and/or their salts, mixtures, alloys.
• A stands for methylammonium MA + (CH 3 NH 3 + ), formamidinium, FA + ((NH 2 ) 2 CH + ), guanidinium Gua (
• Methods for bringing together the components AB - nB 2 and D can be different: dip- coating - dropping one substance onto another or immersing the substance D in the composition AB - nB 2 , spray-coating - spraying one substance onto another, spin coating - applying one substance in a liquid state on a rotating substrate with another substance, doctor blade - applying one substance onto another by means of a dosing blade, roll-to-roll - roll-to-roll technology of application of substances, screen printing - screen printing of the substance AB-nB 2 on the surface of the substance D.
• Excess of the component B can be removed by one of the following methods: washing in a solvent, dropping the solvent on the surface, annealing at an elevated temperature, evaporation under reduced pressure, using a substance that absorbs component B 2 .
• composition and the method for its preparation is achieved by mixing the two solid components AB and B 2 in the form of powders to obtain a liquid composition AB-nB 2 of variable composition with various molar ratios of the components AB and B 2 , where n>l,
• A stands for methylammonium MA + (CH 3 NH3 + ), formamidinium, FA + ((NH ) 2 CH + ), guanidinium Gua (C(NH 2 ) 3 + ), cesium Cs + or a mixture thereof
• B stands for CI " , Br " , ⁇ or a mixture thereof
• B 2 stands for Cl 2 , Br 2 , 1 2 or a mixture thereof.
• a more general approach to produce a light absorbing material with perovskite structure and chemical formula ADB 3 (wherein A is chosen from the cations CH 3 NH 3 + , (NH 2 ) 2 CH + , C(NH 2 ) 3 + , Cs + and the mixtures of thereof, B is chosen from the from the anions CI “ , Br " , ⁇ or mixtures of thereof and D is chosen from elements Sn, Pb, Bi or mixtures of thereof) is to mix the composition AB - nB 2 and reagent that contains D, wherein the component that contains D is chosen from elemental Sn, Pb, Bi and/or their salts, mixtures, alloys, B is chosen from Cl 2 , Br 2 , I 2 and mixtures of thereof, for which, the reactant with the composition AB - nl 2 (n>l) is brought into contact with the component D and the excess of this composition is removed.
• the mixing of the composition AB - nB 2 with the reagent that contains D is performed by means of dissolution of D in the mixture that contains components A and B with a consequent thermal treatment or the mixing of the composition AB - nB 2 with the reagent that contains D is performed by means of dissolution of D in the mixture that contains components A and B with a consequent pressure decrease or the mixing of the composition AB - nB 2 with the reagent D is performed by means of dissolution of D in the mixture that contains components A, B and D with the consequent with a consequent thermal treatment or the mixing of the composition AB - nB 2 with the reagent D is performed by means of dissolution of D in the mixture that contains components A, B and D with a consequent pressure decrease.
• the mixing of reagents AB-nB 2 and the reagent that contains D can be performed by means of any of the methods listed below or a combination thereof: spin-coating, spray-coating, immersion, blade coating, drop-casting, roll-to-roll deposition, screen printing, while the excess of the component B from the composition AB-nB 2 is removed by means of any of the methods listed below or a combination thereof: washing with a solvent, thermal treatment of the substrate, removal under the reduced pressure, removal using sorbent.
• the method for preparation of a liquid reagent for the fabrication of an organic-inorganic perovskite is to mix the components that contain cations A and B within the temperature range from 0 to 150 °C that results in the formation of the mixture AB-nB 2 , (n>l), wherein A is chosen from CH 3 NH 3 + , (NH 2 ) 2 CH + , C(NH 2 ) 3 + , or mixture of thereof, B is chosen from CI " , Br " , ⁇ anions or mixture of thereof, as well as a mixture of these components with Cs + ions while the A to B ratio lies within the range from 1 : 1 to 1 : 5.
• a reagent MAI-2I 2 is obtained by mixing 159 mg MAI and 508 mg I 2 which is then spin-coated on top of the substrate of the following configuration: FTO/Ti0 2 /Pb with a metallic lead layer 250nm thick (FTO stands for fluorine-doped tin oxide). The substrate is then heated and kept at a temperature of 115 °C for 30 minutes. As a result, a perovskite layer MAPbI 3 is formed on the substrate.
• FTO fluorine-doped tin oxide
• the mixture is then filtered using the syringe filter (PTFE, 0.45 ⁇ pore-diameter) and spin-coated on top of metallic lead 50nm-thick on glass substrate. After the spin-coating process, the substrate is immersed into the isopropanol bath, removed and dried. As a result, a perovskite layer MAPbI x Br 3-x is formed on the glass substrate.
• Example 4 1016 mg (4 mmol) of crystalline iodine in the form of a solid powder is added at room temperature to 318 mg (2 mmol) of crystalline MAI in the form of a solid powder. After that, the mixture is stirred for 3 minutes at room temperature, resulting in the formation of a dark brown liquid with a composition MAI-2I 2 . After preparation, the composition retains its properties for at least a month at room temperature.

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• Chemical & Material Sciences (AREA)
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• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Inorganic Chemistry (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Photovoltaic Devices (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Luminescent Compositions (AREA)

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• 2017
  • 2017-12-18 US US16/475,017 patent/US11485748B2/en active Active
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