WO2017121984A1 - Matériaux composites polymère photoactif-pérovskite - Google Patents

Matériaux composites polymère photoactif-pérovskite Download PDF

Info

Publication number
WO2017121984A1
WO2017121984A1 PCT/GB2016/054034 GB2016054034W WO2017121984A1 WO 2017121984 A1 WO2017121984 A1 WO 2017121984A1 GB 2016054034 W GB2016054034 W GB 2016054034W WO 2017121984 A1 WO2017121984 A1 WO 2017121984A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
perovskite
composite material
polymer
poly
Prior art date
Application number
PCT/GB2016/054034
Other languages
English (en)
Inventor
Heming Wang
Original Assignee
Sheffield Hallam University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB1600577.9A external-priority patent/GB201600577D0/en
Priority claimed from GBGB1611540.4A external-priority patent/GB201611540D0/en
Application filed by Sheffield Hallam University filed Critical Sheffield Hallam University
Publication of WO2017121984A1 publication Critical patent/WO2017121984A1/fr

Links

Classifications

    • 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
    • H10K30/352—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 the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer
    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to photoactive polymer-perovskite composite materials, photosensitive optoelectronic devices that incorporate such composite materials and methods of manufacturing such composites and devices.
  • PV cells that convert sunlight into electricity are continuing to attract significant interest as a harvesting tool for renewable energy.
  • photoactive elements for the majority of PV cells are based on crystalline Si, photo-crystalline thin films and metal sulphides. More recently, organic-inorganic triiodide lead based perovskite based semiconductors have emerged into the PV field. Example disclosures can be found in WO 2013/171518; WO 2013/171517; WO 2014/045021 and WO
  • the objectives are achieved via a photoactive composite material that includes an organometallic or inorganic halide perovskite or organometallic and inorganic hybrid halide perovskite in combination with a semiconducting photoactive polymer.
  • a photoactive, light harvesting, electrically conducting composite layer of the present material provides a highly efficient, stable and optionally environmentally benign component for a solar cell that exhibits enhanced capability of converting sunlight into electricity.
  • photoactive polymer being a ' charge distributor' encompasses the photoactive polymer capable of functioning as an electron donor, an electron acceptor or an electron donor and electron acceptor.
  • the photoactive polymer is selected based on its LUMO and HUMO configurations such that photon excitation of an electron from the LUMO to the HUMO provides the desired energy release which is in turn transferred to the perovskite to enhance the semiconducting characteristics of the perovskite.
  • the composite material, formed as a layer is preferably configured as a p-type component within a PV device that when coupled with an n-type material (e.g., Ti0 2 , fullerene PCBM, or poly[[N,N0-bis
  • an n-type material e.g., Ti0 2 , fullerene PCBM, or poly[[N,N0-bis
  • P(NDI2HD-T) (2-hexyldecyl)-naphthalene-l ,4,5,8-bis(dicarboximide)-2,6-diyl]-alt- 5,50-thiophene]
  • P(NDI2HD-T) creates a planar heteroj unction (PHJ) that exhibits high PCE and good stability.
  • the present material is fully compatible with existing material layers of conventional PV devices and accordingly provides Pb-free devices that may incorporate hole-blocking and/or electron-blocking layers to enhance the PCE and the stability of PV devices.
  • a photoactive composite material comprising: an organometallic halide perovskite. inorganic halide perovskite or organometallic and inorganic hybrid halide perovskite; and at least one semiconducting photoactive polymer distributed within the material.
  • Reference within this specification to a 'photoactive composite material ' encompasses a material in which the photoactive polymer is not hybridised or in any way chemically bonded to the perovskite such that the photoactive polymer within the resulting material is a separate species to the perovskite.
  • the composite material may be regarded as a continuous phase or network defined by the perovskite within and around which the photoactive polymer is located.
  • the photoactive polymer may be considered as providing charge distribution or charge transfer between regions of the perovskite network. That is, the photoactive polymer within the present composite material may be considered to be a free or mobile species that is not chemically integrated with the perovskite.
  • the photoactive polymer within the composite structure may be positionally interconnected (but not chemically bonded) with the perovskite and/or with other components or species within the composite structure.
  • the present perovskite-photoactive polymer composite created via the present two-step processing method provides a continuous-phase interconnected structure.
  • a photoactive polymer encompasses a polymer and a polymer species including homopolymers, copolymers, alternating copolymers, periodic copolymers, random copolymers, block copolymers and graft or grafted copolymers.
  • the term encompasses photosensitive polymers (including specifically conjugated polymer species) configured to receive electromagnetic radiation (in the form of UV, visible and near-infrared light) which is absorbed and then converted to excitation energy to provide an electric charge carrier or carriers.
  • a photoactive composite material encompasses a polymer-perovskite nanocomposite light harvesting material being responsive to electromagnetic radiation to provide carrier species within the material.
  • the composite material is formed as polycrystalline structures optionally being nano-sized polycrystalline blocks with little or no internal or surface defects.
  • the photoactive polymer on exposure to electromagnetic radiation is configured as a charger distributor being a p-type, a n-type or a p-type and a n-type material.
  • the photoactive polymer is distributed randomly within the composite material via a process of complete diffusion of a solution of the polymer within a pre-formed layer of metal halide.
  • the photoactive polymer is distributed uniformly within the material such that substantially all regions of the composite material comprise equal concentrations of the photoactive polymer.
  • the photoactive polymer is positioned immediately adjacent and in contact with the halide perovskite so as to provide charge transfer between the perovskite and the photoactive polymer.
  • the photoactive polymer comprises a conjugated polymer species exhibiting a high absorption of electromagnetic radiation including in particular UV, visible and infrared light. Accordingly, the photoactive polymer is capable of harnessing relatively large amount of sunlight via a relatively small quantities of material.
  • the photoactive conjugated polymer contains main chains of aromatic cycles/rings. The aromatic rings may contain nitrogen (NH or N) and/or sulphur either in or outside the aromatic rings.
  • the photoactive polymer is suitable for blending with an electron-acceptor, electron-donor, hole-blocking and/or electron blocking layer in the fabrication of PV devices to form a PHJ.
  • an electron-acceptor or hole-blocking material/layer comprises any one or a combination of: BCP, P(NDI2HD-T), PCBM, ZnO, TiO x , Cs 2 C0 3 , Nb 2 0 5 .
  • an electron donor or electron-blocking material/layer comprises any one or a combination of: PEDOT:PSS, Mo0 3 , W0 3 , V 2 0 5 , NiO.
  • the photoactive polymer is advantageous as an absorber of electromagnetic radiation to enable organometallic halide perovskites, inorganic halide perovskites or organometallic and inorganic hybrid halide perovskite to be utilised within the composite material that are not necessarily high-efficient photoactive. That is, the halide perovskite may function mainly as a charge carrier to work synergistically with the photoactive polymer.
  • the present composite material may comprise transparent halide perovskites suitable for the manufacture of transparent photoactive/photosensitive layers of material with suitable applications including PV devices, photoconducting cells and photodetectors.
  • the polymer-perovskite composite is further advantageous in that the polymer is configured to work as a barrier to enhance the stability of the perovskite material via the formation of nanocomposite structures resulting in a sealed polymer based solar cell.
  • the photoactive polymer is also compatible with solution based manufacturing methods in which the perovskite nanocomposite may be formed by solution layering onto a substrate.
  • the photoactive polymer is further advantageous to enhance the light absorption of the active layer for harvesting solar energy through the selection of one or a plurality of polymers to cover the full spectrum of useful sunlight beyond the limitations of the organometallic halide perovskite. Accordingly, the photoactive polymer broadens the choice of perovskite material with a view to achieving a low cost, stable and
  • perovskites may be selected based on their capability for long charged diffusion length and mechanical flexibility. Such perovskites may be beneficial when combined with conjugated polymers having relatively short charged diffusion lengths to provide highly efficient solar cells.
  • the present hybrid conjugated polymer-perovskite nanocomposite light harvesting materials may be tailored specifically to provide properties of solar cells particularly suited to the sunlight spectrum within specific geographical locations.
  • the present composite material may function as bulk heteroj unction, a discrete heteroj unction, a graded heterojunction, a continuous heteroj unction or a PHJ device comprising two, three, four, five, six, seven, eight, nine, ten or more than ten layers of materials.
  • the photoactive polymer is dispersed uniformly within the composite material.
  • the nanocomposite material may comprise further additives including any one or a combination of the following set of: a dye; a corrosion inhibitor; a polysiloxane; a silane; a silicate; Si; an antimicrobial agent; silica nanoparticles; an organic-inorganic sol gel derived network comprising Si-C bonds.
  • the photoactive polymer is a p- type material and optionally is a semiconductor material.
  • the perovskite is a p- type material and is a semiconductor material.
  • the perovskite comprises the formula AMX 3 or A 3 M 2 X9, in which A comprises an ammonium group or other nitrogen containing organic cation, M is selected from any one or a combination of Pb, Sn, Ge, Ca, Sr, Cd, Ce, Nd, La, Cu, Ni, Mn, Co, Zn, Fe, Mg, Ba, Si, Ti, Bi, or In, and X is selected from at least one of F, CI, Br or I.
  • the perovskite comprises the formula AMX 3 or A 3 M 2 X9, in which A is a metal element Cs, M is selected from any one or a combination of Pb, Sn, Ge, Ca, Sr, Cd, Ce, Nd, La, Cu, Ni, Mn, Co, Zn, Fe, Mg, Ba, Si, Ti, Bi, or In, and X is selected from at least one of F, CI, Br or I.
  • the perovskite comprises the formula AMX 3 or A 3 M 2 X 9 , in which A comprises Cs and an ammonium group or other nitrogen containing organic cation, M is selected from any one or a combination of Pb, Sn, Ge, Ca, Sr, Cd, Ce, Nd, La, Cu, Ni, Mn, Co, Zn, Fe, Mg, Ba, Si, Ti, Bi, or In, and X is selected from at least one of F, CI, Br or I.
  • the perovskite comprises the formula AMX 3 or A 3 M 2 X9, wherein A comprises the formula (RiR 2 R 3 R4N) + , wherein: Ri is hydrogen, unsubstituted or substituted Ci-C 20 alkyl, or unsubstituted or substituted aryl; R 2 is hydrogen, unsubstituted or substituted O-C 20 alkyl, or unsubstituted or substituted aryl; R 3 is hydrogen, unsubstituted or substituted Ci-C 2 o alkyl, or unsubstituted or substituted aryl; and R4 is hydrogen, unsubstituted or substituted Ci-C 2 o alkyl, or
  • the perovskite comprises the formula AMX 3 or A 3 M 2 X 9 ; wherein A comprises the formula (RsNH ) "1" , wherein: R5 is hydrogen, unsubstituted or substituted Ci-C 20 alkyl.
  • the perovskite comprises the formula AMX 3 or A 3 M 2 X9; wherein A
  • the perovskite is a mixed-halide perovskite comprising two or more different anions different halide anions.
  • the semiconducting polymer is a photosensitizer.
  • the semiconducting polymer is a fully conjugated polymer.
  • the conjugated polymer comprises any one or a combination of the
  • the photoactive conjugated polymers include a family of organic semi conductive material that covers a full range of wavelengths for light
  • the semiconducting polymer comprises any one or a combination of the following:
  • an optoelectronic device comprising: at least one first layer having a n-type material; at least one second layer having a p-type material; and a layer of a photoactive composite material as claimed herein.
  • a thickness of the layer of the composite material is in a range 1 nm to 100 ⁇ ⁇ , 1 nm to 1 ⁇ , 1 nm to 800 nm, 1 nm to 600 nm, 1 nm to 400 nm, 1 nm to 300 nm.
  • the layer of the composite material is incorporated in the device in the form of a substantially planar heteroj unction (PHJ) with the first and second layers.
  • the layer of the composite material is incorporated in the device in the form of a bulk heterojunction.
  • the layer of the composite material is in contact with the n-type layer and the p- type layer
  • the layer of the composite material forms a first planar heterojunction with the first layer and a second planar heterojunction (PHJ) with the second layer.
  • the layer of the composite material forms a first planar heterojunction with the p-type layer and a second planar heterojunction (PHJ) with the n-type layer.
  • the composite material is disposed between the first layer and the second layer.
  • the optoelectronic device further comprises: a first electrode; a second electrode; and wherein the first layer, second layer and the layer of the composite material are disposed between the first and second electrodes; and wherein the second electrode is in contact with a second layer and the first electrode is in contact with the first layer.
  • At least one of the first or second electrodes comprises a transparent or semi- transparent electrically conductive material.
  • the optoelectronic device further comprises a metal oxide layer comprising a material selected from any one or a combination of the following set of: tin oxide; indium tin oxide; zinc oxide; zinc indium oxide; titanium oxide; niobium-doped titanium oxide; silicon-doped zinc oxide; aluminium-doped zinc oxide; indium-doped zinc oxide; gallium- doped zinc oxide.
  • the first layer comprises phenyl-C61 -butyric acid methyl ester (PCBM); and the second layer comprises poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS).
  • PCBM phenyl-C61 -butyric acid methyl ester
  • PDOT:PSS poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
  • the optoelectronic device further comprises a buffer layer of 2,9-dimefhl-4,7- diphenyl- 1 , 10-phenanthroline (BCP).
  • BCP 10-phenanthroline
  • one of the first or second electrodes comprises any one or a combination of the following set of: silver, gold, titanium, tin or aluminium.
  • one of the first or second electrodes comprises a transparent conducting oxide, a thin metal layer or a transparent conducting polymer.
  • a method of forming a photoactive composite material comprising: forming at least one first layer of a first perovskite precursor solution; adding at least one semiconducting photoactive polymer onto the first layer to form at least one second layer; adding a second perovskite precursor solution to the second layer to form at least one third layer; and allowing the second and third layers to defuse into the first layer to form a photoactive organometallic halide perovskite semiconducting polymer composite.
  • the first precursor solution comprises MX 2 and a solvent wherein M is selected from any one or a combination of Pb, Sn, Ge, Ca, Sr, Cd, Cu, Ni, Mn, Co, Zn, Fe, Mg, Ba, Si, Ti, Bi, or In, and X is selected from at least one of F, CI, Br or I.
  • M is selected from any one or a combination of Pb, Sn, Ge, Ca, Sr, Cd, Cu, Ni, Mn, Co, Zn, Fe, Mg, Ba, Si, Ti, Bi, or In
  • X is selected from at least one of F, CI, Br or I.
  • the solvent comprises any one or a combination of the following set of Dimethylformamide (DMF), Dimethyl sulfoxide (DMSO), Y-butyrolactone, acetone, acetyl acetone, ethyl acetoacetate N-Methyl-2-pyrrolidone (NMP), Dimethylacetamide (DMAC), Tetrahydrofuran (THF).
  • the second perovskite precursor solution comprises at least one AX dissolved in a further solvent wherein X is selected from at least one of F, CI, Br or I and A comprises an ammonium group or other nitrogen containing organic cation.
  • the organometallic halide perovskite comprises the formula AMX3, wherein A comprises an ammonium group or other nitrogen containing organic cation, M is selected from any one or a combination of Pb, Sn, Ge, Ca, Sr, Cd, Ce, Nd, La, Cu, Ni, Mn, Co, Zn, Fe, Mg, Ba, Si, Ti, Bi, or In, and X is selected from at least one of F, CI, Br or I.
  • the method comprises adding 1, 8-diodoctane (DIO) to the first perovskite precursor solution.
  • DIO 1, 8-diodoctane
  • the method comprises allowing the first layer of a first perovskite precursor solution, the semiconducting photoactive polymer and the second layer of the second perovskite precursor solution to mix (defuse into one another and/or react) for a time period of 0.01 sec to 120 minutes, 0.01 sec to 80 minutes, 0.01 sec to 40 minutes, 0.01 sec to 20, 1 sec to 10 minutes at a temperature -10-80 °C, 0-40 °C, 0-30 °C or ambient (20-25 °C) to form the photoactive organometallic halide perovskite semiconducting polymer composite.
  • DIO 1, 8-diodoctane
  • a method of manufacturing an optoelectronic device comprising: providing a first electrode; adding a first layer to the first electrode; positioning an organometallic halide perovskite semiconducting polymer composite in contact with the first layer; providing a second layer in contact with the organometallic halide perovskite semiconducting polymer composite to form a planar heteroj unction; adding a third layer to the second layer; and contacting the third layer with a second electrode to form a multilayer optoelectronic device.
  • the organometallic halide perovskite semiconducting polymer composite within the optoelectronic device may be formed as a planar heteroj unction.
  • the organometallic halide perovskite semiconducting polymer composite within the optoelectronic device is formed as a bulk heteroj unction.
  • an optoelectronic device comprising a layer of a photoactive composite material as claimed and described herein, the composite material configured as a bulk heteroj unction.
  • an optoelectronic device comprising a layer of a photoactive composite material as claimed and described herein, the composite material configured as a planar heteroj unction.
  • electron-donor, electron-acceptor, n-type and p-type materials are consistent with conventional polymer solar cell terminology associated with bulk heteroj unction and planar heteroj unction solar cells that comprise electron or hole blocking layers positioned adjacent conducting glass and/or metal electrodes in which charge separation results from light generated excitation.
  • the electron-donor and electron- acceptor species provide charge transport between the electrodes of the cell.
  • the photoactive polymer in the present systems may comprise a generally conjugated polymer processing delocalised ⁇ electrons that result from carbon P orbital hybridisation whereby such ⁇ electrons may be excited by electromagnetic radiation from the polymers highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) which accordingly determines the wavelength of electromagnetic radiation that can be absorbed by the polymer species.
  • HOMO highest occupied molecular orbital
  • LUMO unoccupied molecular orbital
  • Figure 1 is a schematic diagram of a fabrication process of a PV device comprising a semiconducting polymer-perovskite nanocomposite layer according to a specific implementation of the present invention
  • Figure 2 is a light absorption graph of a semiconducting polymer-perovskite
  • Figure 3 are photographs of active layers at ambient environment with ⁇ 35% humidity and light absorbance i) after preparation - top: PTB7, CH 3 NH 3 PbI 3 , and PTB7-CH 3 NH 3 PbI 3 composite and ii) after 168 hours exposure - bottom: PTB7, CH 3 NH 3 PbI 3 , and PTB7- CH 3 NH 3 PbI 3 composite;
  • Figure 4 are FTIR spectra of photoactive thin films of the subject invention and various controls at various conditions;
  • Figure 5 is light absorbance of a PTB7 polymer, a CH 3 NH 3 PbI 3 perovskite, and a PTB7- CH 3 NH 3 PbI 3 composite according to one aspect of the present invention
  • Figures 6a and b are cross section SEM images of photoactive thin films on Si -substrates, respectively: a) CH 3 NH 3 PbI 3 perovskite; b) PTB7- CH 3 NH 3 PbI 3 composite according to one aspect of the present invention;
  • Figure 7 is an energy level schematic diagram of a PV device incorporating a PTB7- CH 3 NH 3 PbI 3 composite according to one aspect of the present invention;
  • Figure 8 is I-V characterisation of a PV device comprising a conducting polymer- perovskite nanocomposite layer based PV cell corresponding to example 2 herein according to a specific implementation of the present invention
  • Figure 9 is I-V characterisation of a PV device comprising a conventional perovskite layer without a photoactive polymer according to example 4 herein;
  • Figure 10 is I-V characterisation of a PV device comprising a conducting polymer- perovskite nanocomposite layer according to examples 1 and 3 in accordance with specific implementations of the present invention;
  • Figure 1 1 is I-V characterisation of a PV device comprising a perovskite composite of example 1 herein and a PV device with a standard perovskite layer according to example 4 herein;
  • Figure 12 is I-V characterisation curves of a PV device comprising a conducting polymer- perovskite nanocomposite layer according to example 1 according to different
  • Figure 13 is XRD patterns of CH 3 NH 3 PbI 3 perovskite and PTB7- CH 3 NH 3 PbI 3 composite thin films; according to one aspect of the present invention.
  • Figure 14a and b are SEM morphologies of photoactive thin films a) CH 3 NH 3 PbI 3 perovskite control; and b) PTB7- CH NH 3 PbI 3 composite according one aspect of the present invention;
  • Figures 15a, b, c and d are performance degradation results of two solar cells including i) a CH 3 NH 3 Pbl3 perovskite control and ii) a PTB7- CH 3 NH 3 PbI 3 composite according one aspect of the present invention under exposure to ambient air against time: a) V oc variation; b) Jsc variation; c) PCE variation; d) FF variation;
  • Figures 16a, b, c and d are performance degradation results of two solar cells including i) a CH 3 NH 3 Pbi3 perovskite control and ii) a PTB7- CH 3 NH 3 PbI 3 composite according one aspect of the present invention under exposure to ambient air with ⁇ 35% humility against time: a) V oc variation; b) J sc variation; c) PCE variation; d) FF variation.
  • Organometallic halide perovskite based devices having a planar heteroj unction (PHJ) structure have been generated from a variety of different techniques including solution processing and in particular a one-step solution deposition method, a one-step co- evaporation method, a one-step solution method and a two-step solution processable method.
  • the two-step solution method is adopted herein and is chosen to better control the morphology of the perovskite-polymer hybrid active layer to provide a homogenous, uniform and large-area thin film that is defect (pin-hole and crack) free.
  • the two-step solution method comprises generating a mixed metal halide (MX 2 ) film coated onto an underlying substrate by spin-coating.
  • MX 2 mixed metal halide
  • a perovskite film is fabricated by applying onto the MX 2 film a solution of the photoactive polymer followed by a modified or unmodified methylammonium halide (MAX) solution, formamidium halide (FAX) solution , Csl solution or selection of MAX, FAX, and Csl mixed solution by various techniques including dynamic or static spin coating, dip coating or vapour-assisted- solution coating.
  • MAX modified or unmodified methylammonium halide
  • FAX formamidium halide
  • Csl solution Csl solution or selection of MAX, FAX, and Csl mixed solution by various techniques including dynamic or static spin coating, dip coating or vapour-assisted- solution coating.
  • DIO 8-diodoctane
  • ITO Indium tin oxide
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
  • a Pbl 2 thin film 102 was prepared on top of the PEDOT:PSS film 101 by the spin- coating method at 5000 rpm at stage 109 using the high-purity supersaturated hot solution and annealed at 70°C for 8 min on the hotplate.
  • a thin film 103 of a semiconducting polymer (PTB-7) was deposited on top of the Pbl 2 layer 102 at stage 1 10 prior to adding a solution of methylammonium iodide (MAI) (at fast rotation at 4000 rpm) at stage 1 1 1 to form a MAI layer 104.
  • the multilayer structure was dried at 70°C for 2 min.
  • the multilayer structure was then heated at 100°C for 2 hr to generate a crystalline perovskite- polymer composite active layer 105 at stage 1 12.
  • a phenyl-C61 -butyric acid methyl ester (PCBM) film 106 was spin coated on top of the perovskite- polymer composite layer at 2000 rpm and then heated at 100°C for 30 min at stage 1 13.
  • a BCP layer 107 was spin coated on top of the PCBM film 106.
  • a gold (Au) metal layer 1 15 was evaporated onto the multilayer structure as a top electrode at stage 1 14.
  • MAI was synthesised in ambient atmosphere at room temperature via chemical reaction of 27 ml methyiamine solution (CH 3 NH 2 , 40 wt.% in methanol, TCI) with 30 ml of hydriodic acid (HI 57 wt.% in water, Aldrich) in a round bottomed flask at 0°C in an ice bath for 2 h.
  • the methyiamine solution was added first into the bottomed flask and then HI was dropwise added in during stirring.
  • MAI precipitates were collected after the solution was transformed into a rotary evaporator and heated at 50°C for 1 h. The white precipitates were washed three times with diethyl ether and finally dried in a vacuum for 24 h.
  • Pbl 2 solution was prepared by dissolving 0.461 g Pbl 2 in 1 ml DMF solvent and stirred at 70°C and then 20 ⁇ of DIO was added into the solution to promote the dissolution of Pbl 2 .
  • the Pbl 2 solution became clear after continuously stirring at 70°C for overnight.
  • PCBM solution was prepared by dissolving 30 mg of PCBM in 1 ml of chlorobenzene. 2 mg of bathocuproine (BCP) plus 20 ⁇ 1M diluted acetic acid was dissolved in 1 ml of methanol to form the BCP solution.
  • BCP bathocuproine
  • a PEDOT: PSS solution was prepared and 20 ⁇ of triton X-100 (nonionic surfactant was added) and then filtered through a 0.45 ⁇ PVDF filter.
  • Example 2 Perovskite-polymer composite with low photoactive polymer concentration.
  • Pbl 2 solution was prepared by dissolving 0.235 g Pbl 2 in 1 ml DMF solvent and stirred at 70°C and then 20 ⁇ of DIO was added into the solution to promote the dissolution of Pbl 2 .
  • the Pbl 2 solution became clear after continuously stirring at 70°C for overnight.
  • 1.0 wt.% MAI solution was then produced by adding MAI in 2-propanol and stirred for 1 h at 70°C.
  • PCBM solution was prepared by dissolving 30 mg of PCBM in 1 ml of chlorobenzene. 2 mg of bathocuproine (BCP) plus 20 ⁇ 1M diluted acetic acid was dissolved in 1 ml of methanol to form the BCP solution.
  • BCP bathocuproine
  • a PEDOT: PSS solution was prepared and 20 ⁇ of triton X-100 (nonionic surfactant was added) and then filtered through a 0.45 ⁇ PVDF filter.
  • a bulk heterojunction structural perovskite-based system was also fabricated by the two- step synthesis as detailed in example 1. However, 1.0 wt.% of PC 6 oBM or phenyl-C71- butyric acid methyl ester (P70BM) was added to the Pbl 2 solution or the MAI solution prior to mixing/layering the Pbl 2 solution or the MAI solution with other components/layers as described referring to figure 1 so as to form a bulk heterojunction active layer system.
  • PC 6 oBM or phenyl-C71- butyric acid methyl ester P70BM
  • a further derivative of PC 6 oBM i.e., A10C60 may be added to either the Pbl 2 or MAI solution so as to form a bulk heterojunction active layer system.
  • a bulk heterojunction perovskite-photoactive polymer PV device may be prepared as described in example 1 in which the Pbl 2 or MAI solutions contain a relative concentration of PC 6 oBM, P70BM or AioC6o (1.0 wt.%) so as to form a bulk heterojunction device.
  • I-V characterisation was performed under the simulated AM 1.5G irradiation (100 mW /cm 2 ) using keithley 2401 sourcemeter in ambient environment.
  • a Schott KG5 colour- filtered Si diode (Hamamatsu SI 133) was utilised to calibrate light intensity of the solar light simulator before J-V measurement were carried out.
  • An aperture of aluminium mask was applied on the PV devices to obtain an active area of 0.04 cm 2 and to prevent any contribution from externally fallen light on the devices.
  • Reflectance FTIR spectra were recorded in the frequency range of 800-4000 cm "1 using Nexus FTIR instruments (Thermo Nicolet corp, USA) with ATR-FTIR spectrometer. FTIR samples were prepared on the Au- coated glass slides.
  • X-ray diffraction (XRD) patterns were obtained using a Philips X'PERT MPD with operational parameters of 40 kV tube voltage and 40 mA tube current. SEM was used to investigate morphologies of the perovskite thin films using a FEI Nova Nano200
  • the results presented here demonstrate the suitability of a photoactive composite material within a PV device to enable high performance solar cells.
  • the present photoactive semiconducting polymer-perovskite composite materials are suitable as light-harvesting layers within a multilayer PV device and in particular to form a charge distributor material to create a PHJ PV device.
  • the present photoactive perovskite-PTB7 nanocomposite exhibits enhanced water/moisture stability over existing PV devices formed from PTB7- free organolead halide perovskites.
  • the photoactive polymer-perovskite layer exhibits enhanced light absorption over an extended wavelength (nm) relative to conventional polymer-free perovskites.
  • the light absorption of a conventional polymer-free perovskite 200 decreases as the wave number increases.
  • the light absorption capability of a photoactive polymer 201 in combination with the perovskite 200 to form a hybrid composite material exhibits enhanced light absorption 202.
  • Such configuration provides an active layer covering an enhanced wavelength of
  • Figure 3 represents photographs of thin films and light absorbance of ⁇ 3 ⁇ 3 ⁇ 3 , PTB7- CH 3 NH 3 PbI 3 and PTB7 composite of example 1 in the wavelength range of 400 to 800 nm on glass substrates, respectively.
  • Tremendous enhancement in stability of CH 3 NH 3 PbI 3 perovskite due to forming the PTB7- CH 3 NH 3 PbI 3 composite material was verified after samples of PTB7, CH 3 NH 3 PbI , and PTB7- CH 3 NH 3 PbI 3 composite were left at ambient environment with -35% humidity.
  • ATR-FTIR spectra was recorded for photoactive thin films (according to example 1) as shown in figure 4 where 210 is PTB7 only Polymer after preparation; 21 1 is PTB7- CH 3 NH 3 PbI 3 after 168h exposure; 212 is PTB7-CH 3 NH 3 PbI 3 after 48h exposure; 213 is PTB7-CH 3 NH 3 PbI 3 after preparation; 214 is CH 3 NH 3 PbI 3 control Perovskite after 3h exposure and; 215 is CH 3 NH3Pbl3 control Perovskite after preparation.
  • CH3NH 3 Pbi3 Perovskite and PTB7-CH 3 NH 3 Pbl3 composite thin films illustrate main characteristic peaks of lead perovskite crystals; i.e. wide strong peak at -910 cm “1 for CH 3 - NH3 rock, peak at -989 cm “1 for C-N stretch, peaks at -1403 cm “1 and -1439 cm “1 for C-H vibration bands, and peaks at -1482 cm “1 and - 1570 cm “1 for H-N vibration bands.
  • Most vibrational peaks for the pure CH 3 NH 3 Pbl3 perovskite either disappeared or became weak after exposure for 3 hr under ambient air although the dark colour of the film observed no change.
  • the PTB7-CH 3 NH 3 PbI 3 composite thin film maintained its vibrational peaks with only slightly reduced intensity after 48 hr exposure to ambient environment. Its vibrational peaks disappeared after 168 hr exposure under ambient air, presenting the same FTIR spectrum as that of the pure PTB7 film. However, no colour change was revealed.
  • FIG. 7 illustrates the operation mode of the PTB7- CH3NH3Pbl3 composite-based PV device and the energy levels of each component layer in the device.
  • PTB7 and CHsN Pbb absorb the UV-vis solar radiation and generate excitons, which can be dissociated into free holes and electrons at the interfaces of PTB7/CH3NH3PM3, PEDOT:PSS/CH 3 NH 3 Pbl3, and CH 3 NH 3 PbI 3 /PCBM, respectively.
  • the BCP layer is used as a buffer layer to form good contact with the Au electrode for electrons collection. Holes generated by PTB7 and CH 3 NH 3 PbI 3 are efficiently collected at the anode due to high hole mobility of perovskite and negligible energy level difference between the highest occupied molecular orbital of PTB7 and the valence band of CH 3 NH 3 PbI 3 perovskite.
  • figure 9 is an I-V characterisation of a PV device incorporating a standard perovskite active layer (according to example 4 herein).
  • the degradation of the active layer was recorded in the first day 300; after one day 301 ; after three days 302 and after four days 303.
  • the degradation of the perovskite only active layer was recorded for the first day 400; after one day 401 ; after three days 402 and after four days 403.
  • PCE power-conversion efficiency
  • FIG. 10 illustrates an I-V characterisation of the photoactive composite material of example 1 and example 3 herein to determine the PCE performing of a photovoltaic device as a function of concentration/thickness of the photoactive polymer where curve 501 corresponds to example 1 herein and curve 500 corresponds to example 3 herein.
  • the important parameters from the I-V curve include i) the highest current density (J sc ); ii) the highest open-circuit voltage (Voc) and iii) the fill factor.
  • the PCE performance of the PV device comprising an active layer of example 1 is better than the PV device according to example 3 (curve 500).
  • the larger the enclosed area by the curve and the x-y axis the higher the PCE of the PV device.
  • the fill factor is equal to the ratio of the area enclosed by the curve and the x-y axis to a rectangular area as defined by point lines 502 and the x-y axis as detailed in figure 10.
  • curve 501 comprises the larger fill factor, higher V oc , higher J sc and hence provides PV devices having higher PCE. It was noted that the thickness of the polymer active layer in the PV device of curve 500 was greater than that of the polymer active layer of curve 501.
  • the polymer layer 103 not diffusing fully into (or mixing with) the perovskite (the product after reaction from precursor layers 104 and 102) to form a complete photoactive nanocomposite thin film 105 (i.e. potentially creating a thin un-mixed polymer layer on top of the as-formed nanocomposite layer).
  • This may explain the much poorer PCE performance of the PV device of example 3 relative to that of example 1.
  • the photoactive polymer should be mixed with the PCBM to form a bulk heteroj unction (BHJ) device in order to reduce recombination of positive and negative charges (recombination will result in the low fill factor) and hence obtain a high fill factor and high PCE.
  • BHJ bulk heteroj unction
  • the PCE performance of the present composite (according to example 1) within a solar cell was investigated further relative to a CH 3 NH 3 PbI 3 control via J-V curves and external quantum efficiency (EQE) spectra.
  • the results are shown in tables 1 and 2.
  • Figure 1 1 illustrates the corresponding I-V curves of PV devices according to example 1 (curve 601) and example 4 (curve 600).
  • the PCE of the hybrid photoactive polymer-perovskite-based PV devices is not affected by the incorporation of the photoactive polymer compared to the standard PV devices without the photoactive polymer.
  • I-V curves were obtained for a PV device comprising the photoactive polymer PTB7-perovskite composite layer according to example 1 to determine the PCE performance as a function of reaction time by which the photoactive polymer film 103 was allowed the MAI solution 104 to defuse/react with the Pbl 2 film 102 once immediately after the MAI solution 104 was layered onto film 103.
  • Curve 700 corresponds to a reaction time of 90 seconds and curve 701 corresponds to a reaction time of 120 seconds. It will be noted that the PCE is lower for the shorter waiting time confirming that insufficient time to allow diffusion of the MAI solution 104 and a complete reaction between the MAI and the Pbl 2 film 102 and therefore resulting in that the photoactive polymer does not fully mix with the perovskite is detrimental to PCE. Accordingly, it is an objective based on the results of figure 12 to enable the complete reaction between the MAI and the Pbl 2 film 102 to form the perovskite and to mix the photoactive polymer so as to be homogenously distributed within the perovskite composite layer in order to optimise PCE performance.
  • the stability of the composite of example 1 relative to the CH 3 NH 3 PbI 3 control was then investigated under dark conditions and the results are shown in figures 15a, b, c and d.
  • the PTB7-CH 3 NH 3 PbI 3 composite based solar cells (450) show significantly enhanced stability relative to the CH 3 NH 3 PbI 3 based solar cells (451) since the PTB7- CH 3 NH 3 PbI 3 composite film exhibited a greatly increased resistance against decomposition of the CH 3 NH 3 PbI 3 perovskite as previously shown in Figure 3.
  • V oc of the PTB7-CH 3 NH 3 PbI 3 based solar cells maintained its original value after 920-hour-storage while V 0 c of the CH 3 NH 3 PbI 3 based solar cells started reducing after 360-hour-storage and dropped to -90% of its original value only after 528-hour-storage (figure 15a).
  • J sc of the PTB7-CH3NH3PDI3 based solar cells presented no change before 528-hour-storage and -93% of its original value even after 920-hour-storage (figure 15b).
  • FF variations of the PTB7-CH3NH 3 PbI 3 based solar cells kept within more than 90% of its original value in the storage period while a gradually reduced FF of the CH 3 NH 3 PbI 3 based solar cells was noted, revealing only -47% of its original value after 528-hour- storage. Accordingly, one of the main factors on degradation performance of the present solar cells is considered to be the decrease of J sc that could be caused by alternation or decomposition of CH3NH3PM3 perovskite in the photoactive layer.
  • FTIR spectra illustrate that vibration bands in the N3 ⁇ 4CH 3 organic groups in iodide lead perovskite structures were significantly enhanced by forming nanocomposites with the photoactive polymer PTB7. Further observation of morphologies by both SEM and AFM images suggest that the PTB7 polymer likely persists on the surfaces of CH 3 NH3Pbl3 grains, which creates a barrier layer and acts to protect the CH3NH 3 PbI 3 perovskite.
  • CH3NH 3 Pbl3 as detailed herein was estimated to be 1 :80.
  • the concentration of PTB7 in the PTB7-CH 3 NH 3 PbI 3 composite can be increased and therefore there is a great potential to enhance the stability of PTB7-CH 3 NH 3 PbI 3 composite-based solar cells.
  • the present invention provides the fabrication of organic-inorganic hybrid solution- processed solar cells via blends of PTB7 polymer and CH 3 NH 3 PbI 3 perovskite to function as a light-absorbing layer.
  • the present PHJ PV devices fabricated from CH 3 NH 3 PbI 3 perovskite or PTB7-CH 3 NH 3 PbI 3 composite with PCBM illustrate the same level of PCE.
  • the present photoactive systems are suitable of incorporating a variety of different family materials including photoactive conjugated polymers or organometal halide perovskites to provide high performance and low-cost organic-inorganic hybrid solar cells.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Matériau composite polymère photoactif-pérovskite destiné à être utilisé avec des dispositifs optoélectroniques photosensibles et en particulier des cellules photovoltaïques pour convertir la lumière du soleil en électricité.
PCT/GB2016/054034 2016-01-12 2016-12-22 Matériaux composites polymère photoactif-pérovskite WO2017121984A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB1600577.9 2016-01-12
GBGB1600577.9A GB201600577D0 (en) 2016-01-12 2016-01-12 Photoactive polymer-perovskite composite materials
GBGB1611540.4A GB201611540D0 (en) 2016-07-01 2016-07-01 Photoactive polymer-perovskite composite materials
GB1611540.4 2016-07-01

Publications (1)

Publication Number Publication Date
WO2017121984A1 true WO2017121984A1 (fr) 2017-07-20

Family

ID=57714622

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2016/054034 WO2017121984A1 (fr) 2016-01-12 2016-12-22 Matériaux composites polymère photoactif-pérovskite

Country Status (1)

Country Link
WO (1) WO2017121984A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108493343A (zh) * 2018-04-04 2018-09-04 清华大学 一种钙钛矿薄膜及其制备方法以及该薄膜在光电器件中的应用
CN109216553A (zh) * 2018-07-25 2019-01-15 华南理工大学 一种CsSnI3掺杂有机太阳能电池及其制备方法
CN109216563A (zh) * 2018-07-25 2019-01-15 华南理工大学 一种Cs2SnI6掺杂有机太阳能电池及其制备方法
CN109244240A (zh) * 2018-07-25 2019-01-18 华南理工大学 一种CsGeI3掺杂有机太阳能电池及其制备方法
CN109244241A (zh) * 2018-07-25 2019-01-18 华南理工大学 一种CSPbBr3掺杂有机太阳能电池及其制备方法
CN109273601A (zh) * 2018-09-06 2019-01-25 华中科技大学 一种钙钛矿太阳能电池及其制备方法
CN109346604A (zh) * 2018-09-19 2019-02-15 浙江师范大学 一种钙钛矿太阳能电池
WO2019059270A1 (fr) * 2017-09-21 2019-03-28 積水化学工業株式会社 Cellule solaire
KR20190084815A (ko) * 2018-01-09 2019-07-17 광주과학기술원 페로브스카이트가 내장된 광결정 및 그 제조 방법
CN110085745A (zh) * 2019-04-11 2019-08-02 宁波大学 一种高替代率高效钙钛矿太阳能电池及其制备方法
CN110649162A (zh) * 2019-09-25 2020-01-03 苏州大学 一种宽光谱自驱动无机钙钛矿光电探测器及其制备方法
EP3496172A4 (fr) * 2016-08-02 2020-03-18 Sekisui Chemical Co., Ltd. Élément de conversion photoélectrique de type à jonction solide, film de pérovskite et module de conversion photoélectrique
EP3836218A1 (fr) * 2019-12-12 2021-06-16 Commissariat à l'Energie Atomique et aux Energies Alternatives Couche composite perovskite/materiau de type p ou de type n dans un dispositif photovoltaïque
EP3916819A1 (fr) * 2020-05-29 2021-12-01 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Couche de pérovskite
CN115109233A (zh) * 2021-03-19 2022-09-27 华南理工大学 一种高效稳定聚合物空穴传输层材料和钙钛矿太阳电池器件及其制备方法
WO2022221246A1 (fr) * 2021-04-13 2022-10-20 Applied Materials, Inc. Procédé de formation d'un film de pérovskite contenant un halogénure
US11512213B2 (en) 2018-03-13 2022-11-29 National University Of Singapore Perovskite polymer composite
CN117956812A (zh) * 2024-03-27 2024-04-30 合肥市旭熠科技有限公司 一种复合型钙钛矿厚膜x射线探测器的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008227330A (ja) * 2007-03-15 2008-09-25 Canon Inc 発光素子
KR20150125598A (ko) * 2014-04-30 2015-11-09 주식회사 엘지화학 태양전지 및 이의 제조방법
WO2016083783A1 (fr) * 2014-11-28 2016-06-02 Cambridge Enterprise Limited Dispositif électroluminescent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008227330A (ja) * 2007-03-15 2008-09-25 Canon Inc 発光素子
KR20150125598A (ko) * 2014-04-30 2015-11-09 주식회사 엘지화학 태양전지 및 이의 제조방법
WO2016083783A1 (fr) * 2014-11-28 2016-06-02 Cambridge Enterprise Limited Dispositif électroluminescent

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
D. P. MCMEEKIN ET AL: "A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells", SCIENCE, vol. 351, no. 6269, 8 January 2016 (2016-01-08), pages 151 - 155, XP055298267, ISSN: 0036-8075, DOI: 10.1126/science.aad5845 *
QIFAN XUE ET AL: "Metallohalide perovskite-polymer composite film for hybrid planar heterojunction solar cells", RSC ADV., vol. 5, no. 1, 25 November 2014 (2014-11-25), pages 775 - 783, XP055354325, DOI: 10.1039/C4RA11739E *
SOFIA MASI ET AL: "Growing perovskite into polymers for easy-processable optoelectronic devices", SCIENTIFIC REPORTS, vol. 5, 12 January 2015 (2015-01-12), pages 7725, XP055354326, DOI: 10.1038/srep07725 *
YICHUAN LING ET AL: "Bright Light-Emitting Diodes Based on Organometal Halide Perovskite Nanoplatelets", ADVANCED MATERIALS, vol. 28, no. 2, 17 November 2015 (2015-11-17), DE, pages 305 - 311, XP055328245, ISSN: 0935-9648, DOI: 10.1002/adma.201503954 *
YI-FANG CHIANG ET AL: "High voltage and efficient bilayer heterojunction solar cells based on an organic-inorganic hybrid perovskite absorber with a low-cost flexible substrate", PHYSICAL CHEMISTRY CHEMICAL PHYSICS, vol. 16, no. 13, 5 January 2014 (2014-01-05), pages 6033, XP055109532, ISSN: 1463-9076, DOI: 10.1039/c4cp00298a *
ZIYONG CHENG ET AL: "Layered organic-inorganic hybrid perovskites: structure, optical properties, film preparation, patterning and templating engineering", CRYSTENGCOMM, vol. 12, no. 10, 6 July 2010 (2010-07-06), pages 2646, XP055045568, ISSN: 1466-8033, DOI: 10.1039/c001929a *

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3496172A4 (fr) * 2016-08-02 2020-03-18 Sekisui Chemical Co., Ltd. Élément de conversion photoélectrique de type à jonction solide, film de pérovskite et module de conversion photoélectrique
US11482672B2 (en) 2016-08-02 2022-10-25 Sekisui Chemical Co., Ltd. Solid junction-type photoelectric conversion element, perovskite film, and photoelectric conversion module
JPWO2019059270A1 (ja) * 2017-09-21 2020-09-03 積水化学工業株式会社 太陽電池
CN110785865B (zh) * 2017-09-21 2023-08-11 积水化学工业株式会社 太阳能电池
CN110785865A (zh) * 2017-09-21 2020-02-11 积水化学工业株式会社 太阳能电池
JP7160820B2 (ja) 2017-09-21 2022-10-25 積水化学工業株式会社 太陽電池
US11335514B2 (en) 2017-09-21 2022-05-17 Sekisui Chemical Co., Ltd. Solar cell
WO2019059270A1 (fr) * 2017-09-21 2019-03-28 積水化学工業株式会社 Cellule solaire
KR102469982B1 (ko) 2018-01-09 2022-11-23 광주과학기술원 페로브스카이트가 내장된 광결정 및 그 제조 방법
WO2019139352A1 (fr) * 2018-01-09 2019-07-18 광주과학기술원 Cristal photonique intégré à la pérovskite et procédé de fabrication associé
KR20190084815A (ko) * 2018-01-09 2019-07-17 광주과학기술원 페로브스카이트가 내장된 광결정 및 그 제조 방법
US11512213B2 (en) 2018-03-13 2022-11-29 National University Of Singapore Perovskite polymer composite
CN108493343A (zh) * 2018-04-04 2018-09-04 清华大学 一种钙钛矿薄膜及其制备方法以及该薄膜在光电器件中的应用
CN109216553B (zh) * 2018-07-25 2020-09-22 华南理工大学 一种CsSnI3掺杂有机太阳能电池及其制备方法
CN109216553A (zh) * 2018-07-25 2019-01-15 华南理工大学 一种CsSnI3掺杂有机太阳能电池及其制备方法
CN109216563B (zh) * 2018-07-25 2020-09-22 华南理工大学 一种Cs2SnI6掺杂有机太阳能电池及其制备方法
CN109244241B (zh) * 2018-07-25 2021-05-14 华南理工大学 一种CSPbBr3掺杂有机太阳能电池及其制备方法
CN109216563A (zh) * 2018-07-25 2019-01-15 华南理工大学 一种Cs2SnI6掺杂有机太阳能电池及其制备方法
CN109244240A (zh) * 2018-07-25 2019-01-18 华南理工大学 一种CsGeI3掺杂有机太阳能电池及其制备方法
CN109244241A (zh) * 2018-07-25 2019-01-18 华南理工大学 一种CSPbBr3掺杂有机太阳能电池及其制备方法
CN109244240B (zh) * 2018-07-25 2020-06-19 华南理工大学 一种CsGeI3掺杂有机太阳能电池及其制备方法
CN109273601A (zh) * 2018-09-06 2019-01-25 华中科技大学 一种钙钛矿太阳能电池及其制备方法
CN109346604A (zh) * 2018-09-19 2019-02-15 浙江师范大学 一种钙钛矿太阳能电池
CN110085745A (zh) * 2019-04-11 2019-08-02 宁波大学 一种高替代率高效钙钛矿太阳能电池及其制备方法
CN110085745B (zh) * 2019-04-11 2023-08-01 宁波大学 一种高替代率高效钙钛矿太阳能电池及其制备方法
CN110649162B (zh) * 2019-09-25 2022-09-23 苏州大学 一种宽光谱自驱动无机钙钛矿光电探测器及其制备方法
CN110649162A (zh) * 2019-09-25 2020-01-03 苏州大学 一种宽光谱自驱动无机钙钛矿光电探测器及其制备方法
FR3104816A1 (fr) * 2019-12-12 2021-06-18 Commissariat A L'energie Atomique Et Aux Energies Alternatives Couche composite pérovskite/matériau de type P ou de type N dans un dispositif photovoltaïque
EP3836218A1 (fr) * 2019-12-12 2021-06-16 Commissariat à l'Energie Atomique et aux Energies Alternatives Couche composite perovskite/materiau de type p ou de type n dans un dispositif photovoltaïque
WO2021242108A1 (fr) * 2020-05-29 2021-12-02 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Couche de pérovskite
EP3916819A1 (fr) * 2020-05-29 2021-12-01 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO Couche de pérovskite
CN115109233A (zh) * 2021-03-19 2022-09-27 华南理工大学 一种高效稳定聚合物空穴传输层材料和钙钛矿太阳电池器件及其制备方法
CN115109233B (zh) * 2021-03-19 2023-05-23 华南理工大学 一种高效稳定聚合物空穴传输层材料和钙钛矿太阳电池器件及其制备方法
WO2022221246A1 (fr) * 2021-04-13 2022-10-20 Applied Materials, Inc. Procédé de formation d'un film de pérovskite contenant un halogénure
CN117956812A (zh) * 2024-03-27 2024-04-30 合肥市旭熠科技有限公司 一种复合型钙钛矿厚膜x射线探测器的制备方法

Similar Documents

Publication Publication Date Title
WO2017121984A1 (fr) Matériaux composites polymère photoactif-pérovskite
Rezaee et al. Dopant‐free hole transporting materials for perovskite solar cells
JP6564001B2 (ja) 光吸収構造体が備えられた太陽電池
KR101949641B1 (ko) 페로브스카이트막, 이의 제조방법 및 이를 포함하는 태양전지
US20190228917A1 (en) Inorganic-organic hybrid solar cell having durability and high performance
KR102036239B1 (ko) 와이드 밴드갭을 포함하는 페로브스카이트계 태양전지 및 이의 제조방법
US10714270B2 (en) Photoelectric conversion device and method for manufacturing the same
Yu et al. Application of a new π-conjugated ladder-like polymer in enhancing the stability and efficiency of perovskite solar cells
Suzuki et al. Fabrication and characterization of perovskite type solar cells using phthalocyanine complexes
KR102472294B1 (ko) 향상된 안정성을 갖는 무유기 페로브스카이트 화합물
WO2019232408A1 (fr) Films de pérovskite polycristallin dopé ayant des durées de vie de recombinaison de porteurs de charge étendues et des rendements de conversion de puissance élevés
WO2022061015A1 (fr) Traitements de surface pour films de pérovskite pour améliorer l'efficacité/la stabilité de cellules solaires résultantes
KR102300107B1 (ko) 페로브스카이트 광전 소자의 제조 방법 및 이를 통하여 제조된 페로브스카이트 광전 소자
KR102182902B1 (ko) 태양전지용 투명 전극 및 이를 포함하는 태양전지
EP2544256A1 (fr) Couche de tampon à sélection d'électrons bi-composant et cellules photovoltaïques l'utilisant
KR101997972B1 (ko) 전도성 고분자 화합물, 이를 포함하는 유기태양전지 및 이의 제조방법
KR20230167223A (ko) 대면적 페로브스카이트 박막 형성용 코팅제 및 이를 이용한 대면적 페로브스카이트 박막 형성 방법
KR102462209B1 (ko) 역구조 페로브스카이트 태양전지의 전자전달층용 코팅제 및 역구조 페로브스카이트 태양전지
KR20230052558A (ko) 페로브스카이트 태양전지용 전자전달층 형성 코팅제, 이를 이용한 페로브스카이트 태양전지용 전자전달층 및 이를 포함하는 페로브스카이트 태양전지의 제조방법
KR101880153B1 (ko) 혼성 금속 산화물 및 그 형성 방법과 상기 혼성 금속 산화물을 포함하는 태양 전지
KR102162548B1 (ko) 향상된 안정성과 효율을 갖는 하이브리드 태양전지 및 이의 제조방법
KR102690507B1 (ko) 페로브스카이트 태양전지 및 이의 제조방법
KR102585825B1 (ko) 고내구성 페로브스카이트 광전소자 및 이의 제조방법
EP4325589A1 (fr) Cellule solaire à pérovskite et son procédé de fabrication
KR20220115545A (ko) 전자전달층, 이를 포함하는 페로브스카이트 태양전지 및 이의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16822245

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16822245

Country of ref document: EP

Kind code of ref document: A1