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WO2017009688A1 - Procédé de production de films minces de pérovskite et dispositif optoélectronique - Google Patents

Procédé de production de films minces de pérovskite et dispositif optoélectronique Download PDF

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Publication number
WO2017009688A1
WO2017009688A1 PCT/IB2015/055290 IB2015055290W WO2017009688A1 WO 2017009688 A1 WO2017009688 A1 WO 2017009688A1 IB 2015055290 W IB2015055290 W IB 2015055290W WO 2017009688 A1 WO2017009688 A1 WO 2017009688A1
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Prior art keywords
region
perovskite
divalent
film
layer
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Inventor
Muhammet Erkan KÖSE
Fatih DEĞİRMENCİ
Fatih Mehmet ÇOŞKUN
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Scientific and Technological Research Council of Turkey TUBITAK
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Scientific and Technological Research Council of Turkey TUBITAK
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • 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
    • 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

Definitions

  • the invention relates to processes for producing perovskite layers and processes for producing devices containing perovskite layers.
  • Perovskite layers are useful for light absorbing/emitting optoelectronic devices, transistors, and modulators.
  • Perovskite photovoltaic (PV) technology is one of the most promising solar cell technologies in photovoltaics research due to its high-efficiency and potentially lower production cost of the cells in comparison to other well-known photovoltaic technologies.
  • Perovskites [Mitzi, D. B. et al., Conducting layered organic-inorganic halides containing ⁇ 110>-oriented perovskite sheets. Science, 1995, 267, 1473-1476] are an alternative family of semiconductor materials, which have been investigated for device applications [Mitzi D. B. et al., Organic-inorganic electronics. IBM Journal of Research and Development, 2001, 45, 29- 45]. Kojima et al.
  • a common solvent i.e. ⁇ , ⁇ -dimethylformamide (DMF) or ⁇ -butyrolactone (GBL).
  • DMF ⁇ , ⁇ -dimethylformamide
  • GBL ⁇ -butyrolactone
  • Pbl 2 is first spin-coated from a solution in DMF or dimethyl sulfoxide (DMSO) onto the mesoporous titania film and subsequently transformed into the perovskite by dipping into a solution of methylammonium iodide (MAI), typically in isopropanol. Formation of perovskite is instantaneous within the mesoporous host upon contacting of two components. Burschka et al. demonstrated a PCE of 12.9% by this method.
  • DMSO dimethyl sulfoxide
  • Liu et al. demonstrated a dual source vapor deposition method where PbCl 2 and MAI vapor is deposited onto the substrate at the same time and a PCE figure of 15.4% is achieved. However, this is a high energy-consuming and slow deposition process with respect to the cost-effective and faster solution processing. Chen et al.
  • VASP vapor-assisted solution process
  • the present invention addresses the disadvantages of optoelectronic devices produced by current methods such as low reproducibility, limited substrate choice, and inapplicability to large area.
  • Devices comprising perovskite layer processed from a solution of two precursors lack control of surface morphology and reproducibility.
  • Two-step dipping method works better with devices with a mesoporous Ti0 2 or Alumina scaffold but performs poorly with planar heteroj unction devices.
  • Two-step spin coating method is more advantageous in terms of substrate choice but difficult to adapt to large area substrates due to the spin coating processes involved. VASP seems to address these issues; however, it requires synthesis of large amounts of MAI, which brings forward an additional cost for large scale production.
  • This invention seeks to provide perovskite solar cells with high-efficiency and large area that can be prepared rapidly in an efficient and reproducible way, using readily available low-cost materials, using a short manufacturing procedure based on industrially known manufacturing steps.
  • the invention provides methods comprising: a step of applying and/or depositing a film comprising and/or consisting essentially of one or more divalent or trivalent metal salts; and a step of applying and/or depositing one or more acids and amines/amine derivatives in vapor form either sequentially or simultaneously.
  • the invention provides methods comprising the steps of: a) applying and/or depositing a film comprising and/or consisting essentially of
  • steps a), b), c) and d) may be conducted in any order, either sequentially or simultaneously.
  • the invention provides a method for producing a nanocrystalline organic- inorganic perovskite layer, the method comprising the steps a), b), c), and d) of the invention.
  • the invention provides a method for applying and/or producing a perovskite layer on a surface and/or layer, the method comprising the steps a), b), c), and d) of the invention.
  • the invention provides a method for producing an optoelectronic device, the method comprising the steps a), b), c), and d) of the invention.
  • the invention provides an optoelectronic device comprising a photoactive region, in which photoactive region comprises:
  • an n-type region comprising at least one n-type layer
  • a p-type region comprising at least one p-type layer
  • a layer of a perovskite semiconductor produced by the method comprising the steps a), b), c), and d) of the invention.
  • the optoelectronic device is a photovoltaic device.
  • the optoelectronic device may be other than a photovoltaic device.
  • the optoelectronic device may for instance be a light-emitting device, transistor, or a modulator.
  • the invention provides a process for a photoactive region which comprises:
  • the first region is an n-type region comprising at least one n-type layer and the third region is a p-type region comprising at least one p-type layer;
  • the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer.
  • Perovskite region (second region) can form various junctions with the first and third regions:
  • the perovskite region forms a planar heteroj unction with the first and third regions.
  • porous scaffold which infiltrates into the perovskite region stretching from the first region.
  • the porous scaffold may or may not be made of the same material as the first region.
  • the perovskite region involves a capping layer on top of the porous scaffold, which forms a planar heteroj unction with the third region.
  • porous scaffold which infiltrates into the perovskite region stretching from the first region.
  • the porous scaffold may or may not be made of the same material as the first region.
  • a thin perovskite layer is sensitized on the porous scaffold.
  • Third region infiltrates into said sensitized perovskite layer.
  • the process of the invention is to produce a photovoltaic device comprising said photoactive region.
  • the process may be used to produce an optoelectronic device other than a photovoltaic device, in which optoelectronic device comprises said photoactive region.
  • the process may for instance be used to produce a light-emitting device, transistor, or modulator comprising said photoactive region.
  • the optoelectronic device comprises:
  • steps a), b), c), and d) may be conducted in any order, either sequentially or simultaneously.
  • the first region is n-type and the third region is p-type while in other embodiments the first region is p-type and the third region is n-type.
  • the invention further provides an optoelectronic device, which is obtainable by the process of the invention for producing an optoelectronic device.
  • the optoelectronic device is a photovoltaic device.
  • the optoelectronic device may be other than a photovoltaic device.
  • the optoelectronic device may for instance be a light-emitting device, a transistor, or a modulator.
  • Perovskite region (second region) can form various junctions with the first and third regions:
  • the perovskite region forms a planar heteroj unction with first and third regions.
  • porous scaffold which infiltrates into the perovskite region stretching from the first region.
  • the porous scaffold may or may not be made of the same material as the first region.
  • the perovskite region involves a capping layer on top of the porous scaffold which froms a planar heteroj unction with the third region.
  • porous scaffold which infiltrates into the perovskite region stretching from the first region.
  • the porous scaffold may or may not be made of the same material as the first region.
  • a thin perovskite layer is sensitized on the porous scaffold.
  • Third region infiltrates into said sensitized perovskite layer.
  • Glass/ ⁇ substrate comprises the transparent carrier substrate and the transparent electrode and acts as a support layer for the device.
  • PEDOT:PSS acts as the first region, which is p-type.
  • Perovskite layer is deposited on top of the first region by the methods described elsewhere in this specification.
  • PCBM acts as the third region, which is n-type.
  • the third region may comprise additional layers such as BCP and C60 layers.
  • Aluminum acts as the counter electrode.
  • the device Prior to characterization, the device is encapsulated via resin and the encapsulation glass acts as the top support.
  • FIG. 3 The current density-voltage (J-V) curve of an examplary device. The best device gave a PCE of 9.59% with an open circuit voltage (V oc ) of 0.77 V, a short-circuit density of (Jsc) of -38.1 mA/cm 2 , and FF of 0.33.
  • Figure 4. Optical absorbance of a CH 3 NH 3 PbI 3 film produced by the method of the invention. The extrapolated onset absorption of perovskite film gives a band gap of 1.57 eV, in agreement with the literature reports. The relatively high intensity of peaks at ca. 750 nm and ca. 500 nm indicates good formation of perovskite crystals.
  • FIG. 5 Atomic Force Microscopy image of (a) a neat Pbl 2 film and (b) a CH 3 NH 3 PbI 3 film produced by the method of the invention.
  • the surface roughness (R q ) of the film is mainly limited by the predeposited Pbl 2 film.
  • the R q value for the Pbl 2 film is 6.5 nm whereas R q value for the CH 3 NH 3 PbI 3 film is 8.5 nm.
  • FIG. 6 X-Ray Diffraction spectrum of a CH 3 NH 3 PbI 3 film produced by the method of the invention.
  • the major diffraction peak of the Pbl 2 film was found at 12.8°.
  • CH 3 NH 3 PbI 3 film possesses peaks that can be attributed to either CH 3 NH 3 PbI 3 or Pbl 2 crystals.
  • the diffraction peaks of CH 3 NH 3 PbI 3 crystal at 14.3°, 28.6°, and 43.3° can be assigned to (110), (220), and (330) planes, respectively.
  • the comparison of (110) plane peak of CH 3 NH 3 PbI 3 crystal with respect to strong diffraction plane peak of Pbl 2 crystal can be used to evaluate the extent of perovskite film formation.
  • the present invention encompasses the formation of an organic-inorganic perovskite layer, which is preferably provided on a surface and/or on a layer.
  • perovskite refers to a material with the same type of crystal structure as calcium titanium oxide (CaTi0 3 ), known as the perovskite structure, or ABX 3 , which has a three-dimensional network of corner- sharing BX 6 octahedra.
  • the B component in the ABX 3 structure is a metal cation that can adopt an octahedral coordination of X anions.
  • the A cation is situated in the 12-fold coordinated holes between the BX 6 octahedra and is most commonly inorganic. By replacing the inorganic cation with an organic cation, an organic-inorganic hybrid perovskite can be formed.
  • a 2 BX 4 , ABX 4 and A 3 BX 5 perovskites are also considered members of his family.
  • Other types of organic-inorganic hybrid semiconductors may include crystal structures adopting the formula such as AB 2 X 6 and A 2 BX 6 .
  • the A component in the ABX 3 structure is a monovalent or divalent organic ammonium cation, such as monovalent organic ammonium cation D or divalent organic ammonium cation E as defined below in this specification;
  • the B component in the ABX 3 structure is a divalent or trivalent metal cation, such as divalent metal cation M or trivalent metal cation N as defined below in this specification;
  • the X component in the ABX 3 structure is an anion.
  • the different A cations may be distributed over the A sites in an ordered or disordered way.
  • the different B cations may be distributed over the B sites in an ordered or disordered way.
  • the different X anion may be distributed over the X sites in an ordered or disordered way.
  • the present invention also provides a process for an optoelectronic device comprising a photoactive region involving:
  • an n-type region comprising at least one n-type layer
  • a p-type region comprising at least one p-type layer
  • a layer of a perovskite semiconductor which is produced by:
  • steps a), b), c), and d) may be conducted in any order, either sequentially or simultaneously.
  • the term "acid”, as used herein, refers to an inorganic compound with the formula HX where X is anion of a group 7 element, i.e., of a halogen, or an organic anion such as NCS-, CN-, CH 3 COO-, and NCO-.
  • HX is a hydrogen halide, i.e., hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide. More preferably HX is hydrogen iodide.
  • amines/amine derivative refers to an organic compound with one or more amine groups.
  • Organic compound is preferably in the form of R 1 NH 2 , R 1 R2 NH,
  • amines examples include Ethylamine, methylamine,
  • photoactive region refers to a region in the optoelectronic device which (i) absorbs light, which may then generate free charge carriers; or (ii) accepts charge, both electrons and holes, which may subsequently recombine and emit light; or (iii) changes electrical conductivity by applied bias; or (iv) changes the amplitude of the carrier signal in accordance to the instantaneous amplitude of the modulating signal.
  • semiconductor refers to a material with electrical conductivity intermediate in magnitude between that of a conductor and a dielectric.
  • a semiconductor may be an n-type semiconductor, a p-type semiconductor, or an intrinsic semiconductor.
  • n-type region refers to a region of one or more electron- transporting materials. It may additionally comprise hole-blocking materials, bulk heterojunctions and protective layers.
  • electron-transporting layer refers to a layer of an electron-transporting material.
  • An “electron-transporting material” is any material or composition wherein charges are transported mainly by electron movement across said material or composition.
  • An electron-transporting material could be a single electron- transporting compound or elemental material, or a mixture of two or more electron- transporting compounds or elemental materials.
  • An electron-transporting compound or elemental material may be undoped or doped with one or more dopant elements.
  • hole-blocking layer refers to a layer of a hole-blocking material.
  • a “hole-blocking material” is any material or composition wherein electron movement is allowed and hole movement is partially or fully blocked across said material or composition.
  • a hole-blocking material could be a single hole-blocking compound or elemental material, or a mixture of two or more hole-blocking compounds or elemental materials.
  • a hole-blocking compound or elemental material may be undoped or doped with one or more dopant elements.
  • Bulk heteroj unction and protective layers are defined elsewhere in this specification.
  • the term "p-type region” refers to a region of one or more hole-transporting materials. It may additionally comprise electron-blocking materials, bulk heterojunctions and protective layers.
  • hole-transporting layer refers to a layer of a hole-transporting material.
  • a “hole-transporting material” is any material or composition wherein charges are transported mainly by hole movement across said material or composition.
  • a hole- transporting material could be a single hole-transporting compound or elemental material, or a mixture of two or more hole-transporting compounds or elemental materials.
  • a hole- transporting compound or elemental material may be undoped or doped with one or more dopant elements.
  • electron-blocking layer refers to a layer of an electron- blocking material.
  • An “electron-blocking material” is any material or composition wherein hole movement is allowed and electron movement is partially or fully blocked across said material or composition.
  • An electron-blocking material could be a single electron-blocking compound or elemental material, or a mixture of two or more electron-blocking compounds or elemental materials.
  • An electron-blocking compound or elemental material may be undoped or doped with one or more dopant elements. Bulk heteroj unction and protective layers are defined elsewhere in this specification.
  • the term "bulk heteroj unction” refers to a layer consisting of a nanoscale blend of electron donor and electron acceptor materials.
  • An electron donor is a chemical entity that donates electrons to another compound.
  • An electron acceptor is a chemical entity that accepts electrons transferred to it from another compound.
  • An electron acceptor can be envisioned as a hole donor.
  • Bulk heteroj unction layer absorbs photons and generates electron and hole carriers.
  • a typical bulk heteroj unction layer comprises organic electron-transporting materials and organic hole-transporting materials such as Poly-(3-hexylthiophene-2,5-diyl) (P3HT) and Phenyl-C61 -butyric acid methyl ester (PCBM).
  • the term "protective layer” refers to a layer of semiconducting or thin dielectric layer which allows charge transport. It comprises a conformal coating which is compact enough to avoid short circuits and pin holes between the layers in which said protective layer is placed.
  • the protective layer preferably comprises a metal oxide.
  • the protective layer may comprise or consist essentially of a material selected from Mg-oxide, Hf-oxide, Ga-oxide, In-oxide, Nb-oxide, Ti-oxide, Ta-oxide, Y -oxide and Zr- oxide. Ga-oxide is a preferred material for said protective layer.
  • the protective layer preferably has a thickness of not more than 5 nm, preferably 4 nm or less, even more preferably 3 nm or less, and most preferably 2 nm or less.
  • Said metal "protective layer” is preferably a "buffer layer” and provided by atomic layer deposition (ALD). For example, 2 to 7 layers are deposited by ALD so as to provide said protective layer. Accordingly, said protective layer is preferably a metal oxide multilayer.
  • the invention provides a process for a photoactive region which comprises:
  • steps a), b), c), and d) may be conducted in any order, either sequentially or simultaneously.
  • the first region is an n-type region comprising at least one n-type layer and the third region is a p-type region comprising at least one p-type layer;
  • the first region is a p-type region comprising at least one p-type layer and the third region is an n-type region comprising at least one n-type layer.
  • Perovskite region (second region) can form various junctions with the first and third regions:
  • the perovskite region forms a planar heteroj unction with the first and third regions.
  • porous scaffold which infiltrates into the perovskite region stretching from the first region.
  • the porous scaffold may or may not be made of the same material as the first region.
  • the perovskite region involves a capping layer on top of the porous scaffold which forms a planar heteroj unction with the third region
  • porous scaffold which infiltrates into the perovskite region stretching from the first region.
  • the porous scaffold may or may not be made of the same material as the first region.
  • a thin perovskite layer is sensitized on the porous scaffold.
  • Third region infiltrates into said sensitized perovskite layer.
  • perovskite region (second region) forms the following junctions with the first and third regions:
  • the perovskite region forms a planar heteroj unction with the first and third regions.
  • porous scaffold which infiltrates into the perovskite region stretching from the first region.
  • the porous scaffold may or may not be made of the same material as the first region.
  • the perovskite region involves a capping layer on top of the porous scaffold which forms a planar heteroj unction with the third region
  • the optoelectronic device comprises:
  • steps a), b), c), and d) may be conducted in any order, either sequentially or simultaneously.
  • the first region is n-type and the third region is p-type while in other embodiments the first region is p-type and the third region is n-type.
  • the optoelectronic device of the invention preferably comprises a carrier substrate.
  • the carrier substrate preferably provides the physical support of the device.
  • the carrier substrate preferably provides a protection with respect to physical damage and thus delimits the optoelectronic device with respect to the outside.
  • the optoelectronic device may be constructed by applying the different layers in a sequence of steps, one after the other, onto the carrier substrate.
  • the carrier substrate may thus also serve as a starting support for the fabrication of the optoelectronic device.
  • the carrier substrate is preferably transparent, so as to let light pass through the optoelectronic device.
  • Transparent means transparent to at least a part, preferably a major part of the visible light.
  • the carrier substrate is substantially transparent to all wavelengths or types of visible light.
  • the carrier substrate may be transparent to non-visible light, such as ultraviolet and infrared radiation, for example.
  • a current collector electrode is provided.
  • the electrode layer is preferably transparent. It can replace or contain the carrier substrate as in the case of conductive glass or conductive plastic.
  • transparent electrodes are indium doped tin oxide (ITO), fluorine doped tin-oxide (FTO), ZnO-Ga 2 0 3 , ZnO-Al 2 0 3 , tin-oxide, antimony doped tin oxide (ATO), SrGe0 3 , zinc oxide, silver nanowires, carbon nanotubes, and graphene.
  • the perovskite region forms a planar heteroj unction with the first region.
  • First region can either be n-type or p-type. If the divalent/trivalent metal salt is spin cast from a solvent such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or ⁇ -butyrolactone (GBL), it is preferable that the first region should not be soluble by these solvents.
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • GBL ⁇ -butyrolactone
  • Preferred n-type materials are compact TiO x , ZnO x films and a preferred p-type layer is PEDOT:PSS.
  • porous scaffold between the first region and the perovskite region (second region) which increases the interaction area.
  • a preferred scaffold will be made out of titania and/or alumina nanoparticles.
  • the method of the invention comprises the steps of:
  • steps a), b), c), and d) may be conducted in any order onto the first region, either sequentially or simultaneously.
  • steps a), b), c), and d) are conducted onto the first region in the following order:
  • step a) i.e., applying and/or depositing a film comprising and/or consisting essentially of one or more divalent or trivalent metal salts
  • step b) i.e., applying and/or depositing one or more acids in vapor form
  • step c) i.e., applying and/or depositing one or more amines/amine derivatives in vapor form
  • step b) i.e., applying and/or depositing one or more acids in vapor form
  • step d) i.e., annealing the existing film but the present invention also encompasses, in other embodiments, that step a), b), c), and d) is conducted in any order either sequentially or simultaneously.
  • said one or more divalent or trivalent metal salts in step a) are selected from salts of formula MX 2 or NX 3 wherein:
  • M is a divalent metal cation selected from the group consisting of Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , Pd 2+ , Cd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , Eu 2+ , or Yb 2+ ;
  • N is a trivalent metal cation selected from the group of Bi 3+ and Sb 3+ ; and X is independently selected from F, CI-, Br-, I-, NCS-, CN-, CH 3 COO-, and NCO-.
  • said metal salt is MX 2 .
  • said divalent or trivalent metal salt preferably a divalent metal salt
  • said divalent or trivalent metal salt is a metal halide.
  • the metal ion said divalent or trivalent metal salt is Pb 2+ .
  • the halide in said divalent or trivalent metal salt is ⁇ .
  • the divalent or trivalent metal salt is Pbl 2 .
  • the second salt is Snl 2 .
  • said film comprising said one or more divalent or trivalent metal salt is applied and/or deposited (step a)) by any one or more methods selected from: deposition from solution, deposition from a dispersion, for example, from a colloidal dispersion, deposition by thermal evaporation, deposition by sputtering, electrodeposition, atomic-layer-deposition (ALD), and formation of the metal salt in situ.
  • deposition from solution deposition from a dispersion, for example, from a colloidal dispersion, deposition by thermal evaporation, deposition by sputtering, electrodeposition, atomic-layer-deposition (ALD), and formation of the metal salt in situ.
  • ALD atomic-layer-deposition
  • deposition from solution encompass, for example, drop casting, spin-coating, dip-coating, curtain coating, spray-coating, doctor blading, screen printing and ink-jet printing.
  • said film comprising one or more divalent or trivalent metal salt is applied and/or deposited by spin-coating a solution of one or more said divalent or trivalent metal salts, preferably at 2000 rpm or more, preferably 3000 rpm or more.
  • said spin-coating takes place for 1 s (second) to 10 minutes, preferably 2 s to 30 s.
  • the solvent used for the spin-coating may be any solvent that dissolves the one or more divalent or trivalent metal salts.
  • the metal salt is Pbl 2
  • the solvent is
  • DMF ⁇ , ⁇ -dimethylformamide
  • GBL ⁇ -butyrolactone
  • the concentration of the one or more divalent or trivalent metal salts in the solution used for the spin-coating for obtaining the film comprising the one or more divalent or trivalent metal salt is 50 mg/mL or more, more preferably 250 mg/mL or more.
  • the two different salts may be applied at the same time.
  • the solution may contain different metal salts.
  • Said different metals salts preferably differ with respect to the anion. Accordingly, divalent metals salts or for example
  • divalent metals salts are deposited at the same time, for example are present in the same solution, M being a defined metal and X i , X ii and X iii being different anions selected from the above, preferably different halides.
  • X i , X ii and X iii are ⁇ , CI- and Br-, respectively.
  • the method of the invention comprises the steps of applying and/or depositing a film comprising two or more divalent metal salts selected from M3 ⁇ 4 MX U 2 and MX m 2 , wherein X i , X ii and X iii (charge not shown) are each different anions selected from ⁇ , CI-, Br-, I-, NCS-, CN-, CH 3 COO-, and NCO-, preferably from I-, CI-, and Br-.
  • a mixture of M i X 2 with M ii X or X iii X 3 may be applied, said X i X 2 and one from M ii X andX iii X 3 being preferably applied together/at the same time, for example deposited from the same solution.
  • X i 1 and X iii represent monovalent or trivalent cations.
  • a mixture of metal salts with identical charges M i 2 and M ii X 2 may be applied, said X i X 2 and M ii X 2 being preferably applied together/at the same time, for example deposited from the same solution.
  • X i and X i 1 represent divalent cations, which would be used to engineer the bandgap of the perovskite semiconductor.
  • M ii and M iii will be Pb and Sn.
  • the carrier substrate with the metal salt film is annealed between 50 °C and 140 °C, more preferably at 70 °C.
  • the duration of annealing is between 0 to 1 hours, preferably between 5 minutes to 30 minutes.
  • step b) and step c) is conducted after step a), it preferably comprises or consists essentially of the step of exposing or contacting the film comprising the one or more divalent or trivalent metal salts obtained in step a) to the vapor of one or more acids in step b) and the vapor of one or more amines/amine derivatives in step c).
  • said acid is an inorganic compound with the formula HX where X is anion of a group 7 element, i.e., of a halogen, or an organic anion such as NCS-, CN-, CH 3 COO-, and NCO-.
  • HX is a hydrogen halide, i.e., hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide. More preferably HX is hydrogen iodide.
  • said amines/amine derivative is selected from primary, secondary and tertiary amines ( Preferably amines/amine derivatives are alkyl amines, more preferably, methylamine and formamidine.
  • a mixed perovskite is obtained if the film comprising divalent metal salts in step a) comprises for example, is exposed to an acid in step b),
  • the film comprising divalent metal salts comprises the acid is selected from salts comprising one of the anions contained in the divalent metal salt layer, for example from HX i or HX 11 .
  • the method of the invention comprises the step (e.g. step a)) of applying and/or depositing a film comprising MI 2 and one selected from MC1 2 and MBr 2 .
  • MI 2 and MC1 2 or MI 2 and MBr 2 are deposited from the same solution in which they are dissolved.
  • the method of the invention comprises the step (e.g. step b)) of applying one or more acids in vapor form, preferably HI vapor, and one or more amines/amine derivatives in vapor form onto the divalent metal halides obtained in the previous step.
  • M is Pb and/or amine/amine derivative is methylamine or formamidine.
  • the method of the invention comprises the step (e.g. step a)) of applying and/or depositing a film comprising MC1 2 and one selected from MI 2 and MBr 2 .
  • MC1 2 and MI 2 or MC1 2 and MBr 2 respectively are deposited from the same solution in which they are dissolved.
  • the method of the invention comprises the step (e.g. step b)) of applying one or more acids in vapor form, preferably HI vapor, and one or more amines/amine derivatives in vapor form onto the divalent metal halides obtained in the previous step.
  • M is Pb and/or amine/amine derivative is methylamine or formamidine.
  • step c) comprises applying and/or depositing one single and/or one structurally defined amine/amine derivative.
  • step c) comprises applying and/or depositing one single and/or one structurally defined amine/amine derivative.
  • salt is deposited in step a).
  • the first amine/amine derivative is methylamine
  • the second amine/amine derivative is preferably formamidine.
  • vapors of acids and amines/amine derivatives in steps b) and c) can be obtained in (i) direct form; or (ii) from solutions under reduced pressure; or (iii) by heating the said chemicals in a controlled atmosphere.
  • vapor of one or more acids can be applied directly or with a carrier gas onto the divalent or trivalent metal salt from concentrated or dilute acid solutions.
  • a carrier gas onto the divalent or trivalent metal salt from concentrated or dilute acid solutions.
  • HI vapor is applied from a concentrated HI solution with a concentration ranging from 48% to 67% in water by mass.
  • vapor of one or more amines/amine derivatives can be applied directly or with a carrier gas from concentrated or dilute amine solutions.
  • the amine/amine derivative is methylamine, preferably the weight percent of amine content is larger than 40% by mass in water or methanol.
  • the amine/amine derivative is formamidine, preferably it is applied directly in vapor form.
  • step b) and step c) can both be applied in an open chamber or closed chamber, preferably in a closed chamber.
  • the partial vapor pressures and flow rates of the acid vapors and amine/amine derivative vapors can be varied or fixed, preferably they are fixed.
  • steps b) and c) can be applied in any order either sequentially or simultaneously when applied in a closed chamber with fixed partial pressures and fixed flow rates for the acid vapors, the amines/amine derivative vapors and the corresponding carrier gases (if any).
  • step b) and step c) when step b) and step c) is conducted after step a), they can be applied in any order either sequentially or simultaneously.
  • a step b) is conducted first, followed by step c), which is followed by another step b).
  • the duration of each step depends on the vapor pressure and flow rates of the gases involved.
  • the duration of the step b) is anywhere between 0 seconds to 10 minutes, more preferably between 5 seconds to 2 minutes and the duration of step c) is anywhere between 0 seconds to 10 minutes, more preferably between 0 seconds to 30 seconds.
  • step d) is applied in which the carrier substrate with the perovskite film is annealed between 60 °C and 180 °C, preferably between 90 °C and 120 °C, and more preferably at 100 °C.
  • the duration of step d) is between 0 and 4 hours, preferably between 30 minutes to 2 hours.
  • the organic-inorganic perovskite material that is used and/or obtained in the previous step preferably comprises a perovskite- structure of any one of formulae (I), (II) , (III), (IV), (V) and/or (VI) below:
  • D is a monovalent organic cation
  • E is a divalent organic cation
  • M is a divalent metal cation
  • N is a trivalent metal cation
  • M is Sn 2+ or Pb 2+ , more preferably Pb 2+ .
  • N is preferably selected from the group of Bi 3+ and Sb 3+ .
  • any X and X' may be selected independently from F, CI-, Br-, I-, NCS-, CN-, CH 3 COO , and NCO-.
  • X is halogen, preferably X is selected from Br- or ⁇ , more preferably
  • D x D' ( i_ x) means different monovalent organic D cations may be distributed over the D sites in an ordered or disordered way;
  • E X E' (1-X) means different divalent organic E cations may be distributed over the E sites in an ordered or disordered way means monovalent D cation and divalent E cation may be distributed
  • the perovskite comprises more than one metal cation, means different M cations may be distributed over the M sites in an ordered or disordered way; means different N cations may be distributed over the N sites in an ordered or disordered way.
  • the perovskite comprise more than one X anion, means the different X
  • anions may be distributed over the X sites in an ordered or disordered way.
  • said organic-inorganic perovskite layer comprises a perovskite- structure of any one of the formulae
  • E is preferably C 2 H 4 (NH 3 ) 2 2+ (ethylenediammonium dication)
  • D is preferably CH 3 NH 3 + (methylammonium)
  • D' is an organic cation that enhances perovskite crystallization such as CH(NH 2 ) 2 + (formamidinium).
  • organic monovalent cation D and organic divalent cation E is originated from the amine/amine derivative evaporated in step c) of the invention.
  • Amines/amine derivatives that can be utilized to have monovalent cation D or D' in the final perovskite structure can be selected independently from one of the compounds below:
  • Amines/amine derivatives that can be utilized to have divalent cation E in the final perovskite structure can be selected independently from one of the compounds below:
  • any one of is independently selected from from CI -CI 5 organic substituents comprising from 0 to 15 heteroatoms.
  • any one, several or all hydrogens in said substituent may be replaced by halogen and said organic substituent may comprise up to fifteen (15) N, S or O heteroatoms, and wherein, in any one of the compounds
  • the two or more of substituents present may be covalently connected to each other to form a substituted or unsubstituted ring or ring system.
  • any heteroatom is connected to at least one carbon atom.
  • neighboring heteroatoms are absent and/or heteroatom-heteroatom bonds are absent in said CI -CI 5 organic substituent comprising from
  • any one of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from CI to C15 aliphatic and C4 to C15 aromatic or hetero aromatic substituents, wherein any one, several or all hydrogens in said substituent may be replaced by halogen and wherein, in any one of the compounds (2) to (8), the two or more of the substituents present may be covalently connected to each other to form a substituted or unsubstituted ring or ring system.
  • any one of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from CI to C8 organic substituents comprising, from 0 to 4 N, S and/or O heteroatom, wherein, independently of said N, S or O heteroatoms, any one, several or all hydrogens in said substituent may be replaced by halogen, and wherein two or more of substituents present on the same cation may be covalently connected to each other to form a substituted or unsubstituted ring or ring system.
  • any one of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from CI to C8 aliphatic, C4 to C8 heteroaromatic and C6 to C8 aromatic substituents, wherein said heteroaromatic and aromatic substituents may be further substituted.
  • any one of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from CI to C6 organic substituents comprising, from 0 to 3 N, S and/or O heteroatom, wherein, independently of said N, S or O heteroatoms, any one, several or all hydrogens in said substituent may be replaced by halogen, and wherein two or more of substituents present on the same cation may be covalently connected to each other to form a substituted or unsubstituted ring or ring system.
  • any one of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from CI to C6 aliphatic, C4 to C6 heteroaromatic and C6 to C8 aromatic substituents, wherein said heteroaromatic and aromatic substituents may be further substituted.
  • any one of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected From CI to C4, preferably CI to C3 and most preferably CI to C2 aliphatic substituents wherein any one, several or all hydrogens in said substituent may be replaced by halogen and wherein two or more of substituents present on the same cation may be covalently connected to each other to form a substituted or unsubstituted ring or ring system.
  • any one of R 1 , R 2 , R 3 , R 4 , and R 5 is independently selected from CI to CIO alkyl, C2 to CIO alkenyl, C2 to CIO alkynyl, C4 to CIO heteroaryl and C6 to CIO aryl, wherein said alkyl, alkenyl, and alkynyl, if they comprise 3 or more carbons, may be linear, branched or cyclic, wherein said heteroaryl and aryl may be substituted or unsubstituted, and wherein several or all hydrogens in any one of 5 may
  • any one of is independently selected from CI to C8 alkyl, C2 to C8 alkenyl, C2 to C8 alkynyl, C4 to C8 heteroaryl and C6 to C8 aryl, wherein said alkyl, alkenyl, and alkynyl, if they comprise 3 or more carbons, may be linear, branched or cyclic, wherein said heteroaryl and aryl may be substituted or unsubstituted, and wherein several or all hydrogens in R 1 , R 2 , R 3 , R 4 , and R 5 may be replaced by halogen.
  • any one of is independently selected from CI to C6 alkyl, C2 to C6 alkenyl, C2 to C6 alkynyl, C4 to C6 heteroaryl and C6 aryl, wherein said alkyl, alkenyl, and alkynyl, if they comprise 3 or more carbons, may be linear, branched or cyclic, wherein said heteroaryl and aryl may be substituted or unsubstituted, and wherein several or all hydrogens in R 1 , R 2 , R 3 , R 4 , and R 5 may be replaced by halogen.
  • any one of is independently selected
  • alkyl, alkenyl and alkynyl may be linear, branched or cyclic, and wherein several or all hydrogens in in may be replaced by halogen.
  • any one of independently selected from CI to C3, preferably CI to C2 alkyl, C2 to C3, preferably C2 alkenyl and C2 to C3, preferably C2 alkynyl, wherein said alkyl, alkenyl and alkynyl, if they comprise 3 or more carbons, may be linear, branched or cyclic, and wherein several or all hydrogens in
  • R 4 and R 5 may be replaced by halogen.
  • any one of is independently selected from CI to C4, more preferably CI to C3 and even more preferably CI to C2 alkyl. Most preferably, any one of 5
  • alkyl are methyl. Again, said alkyl may be completely or partially halogenated.
  • said optoelectronic device comprises a third region that is applied/deposited on top of the second region which comprises a perovskite region. Said third region can form various junctions with the perovskite region:
  • the third region forms a planar heteroj unction with a planar perovskite region.
  • the third region forms a planar heteroj unction with the capping layer of a perovskite region.
  • the third region infiltrates into a sensitized perovskite layer.
  • third region forms the following junctions with the perovskite region:
  • the third region forms a planar heteroj unction with a planar perovskite region.
  • the third region forms a planar heteroj unction with the capping layer of a perovskite region.
  • the third region forms a planar heteroj unction with the second region in both cases.
  • the quality of the planar heteroj unction between the perovskite (second) region and the third region is extremely important because any pinholes or cracks on the perovskite surface degrade device performance significantly.
  • the present invention minimizes the said pinholes and cracks on the final perovskite surface, because the quality of the perovskite film is limited by the quality of the Pbl 2 film. Therefore, the present invention allows the fabrication of high- efficiency solar cell with extremely large short circuit current density.
  • the perovskite layer forms a planar heteroj unction with the third region.
  • Third region can either be n-type or p-type.
  • Preferred inorganic n-type materials are compact preferred inorganic p-type materials are CuNCS, Cul,
  • preferred organic n-type materials are fullerene (C60) and Phenyl-C61 -butyric acid methyl ester (PCBM); preferred organic p-type materials are Poly(3-hexylthiophene-2,5- diyl) (P3HT) and Spiro-OMeTAD (2,2',7, 7'-tetrakis-N,N-di-p-methoxyphenylamine-9,9'- spirobifluorene) and derivatives of PTAA (poly (triarly amine)) such as Poly[bis(4phenyl) (2,4,6-trimethylphenyl)amine]) or (Poly[bis( 4-phenyl)( 4-butylphenyl)amine]).
  • organic in expressions "organic n-type material", “organic p-type material”, and the like does not exclude the presence of further components.
  • Further components may be selected from (a) one or more dopants, (b) one or more solvents, (c) one or more other additives such as ionic compounds, and (c) combinations of the aforementioned components, for example.
  • such further components may be present in amounts of 0-30wt.%, 0-20wt.%, 0-10wt.%, most preferably 0-5wt.%.
  • Examples of ionic compounds that may be present in organic hole transport materials are TBAPF ⁇ 5, Na CF 3 SO 3 , Li CF 3 SO 3 , LiC10 4 , and Li[(CF 3 S0 2 ) 2 N.
  • Examples of other compounds that may be present in organic hole transport materials are amines, 4-tertbutylpyridine, 4-nonyl-pyridine, imidazole, N-methyl benzimidazole, for example.
  • the counter electrode is applied/deposited on top of the third region.
  • the counter electrode may form the outmost layer and thus one of the outer surfaces of the cell. It is also possible that a substrate or support layer is present on one side of counter electrode.
  • the counter electrode generally comprises a catalytically active material, suitable to provide electrons and/or fill holes towards the inside of the device.
  • the counter electrode may, for example, comprise one or more materials selected from (the group consisting of) Pt, Au, Ni, Cu, Ag, Al, In, Ru, Pd, Rh, Ir, Os, C, conductive polymer, conductive oxide such as indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), ZnO-Ga 2 0 3 , ZnO-Al 2 0 3 , tin-oxide, antimony doped tin oxide (ATO), SrGe0 3 combination of two or more of the aforementioned, for example.
  • ITO indium doped tin oxide
  • FTO fluorine doped tin oxide
  • ZnO-Ga 2 0 3 ZnO-Al 2 0 3
  • tin-oxide antimony doped tin oxide
  • Conductive polymers may be selected from polymers comprising polyaniline, polypyrrole, polythiophene, polybenzene, polyethylenedioxythiophene, polypropylenedioxy- thiophene, polyacetylene, and combinations of two or more of the aforementioned, for example. Such conductive polymers may be used as hole-transporting materials as well.
  • the counter electrode may be applied as is conventional, for example by thermal evaporation of the counter electrode material onto the third region.
  • the counter electrode is preferably connected to a current collector, which is then connected to the external circuit.
  • a conductive support such as conductive glass or plastic may be electrically connected to the counter electrode on the second side.
  • the solar cell of the invention is preferably a solid state solar cell.
  • the solar cell is preferably (i) planar heteroj unction solar cell or (ii) a solar cell comprising a perovskite region with a capping layer.
  • solar cell exhibits a power conversion efficiency (PCE) of more than 9%, preferably more than 9.5%.
  • PCE is preferably determined as disclosed in the example and under the conditions specified therein.
  • the solar cell preferably exhibits a short circuit current density more than 20 mA/cm , preferably more than
  • Glass/ITO substrate comprises the transparent carrier substrate and the transparent electrode. It acts as a support layer for the device.
  • PEDOT:PSS acts as the first region, which is p-type.
  • Perovskite layer is deposited on top of the first region by the methods described elsewhere in this specification.
  • PCBM acts as the third region, which is n-type.
  • the third region may comprise additional n-type layers such C60 and a hole- blocking layer such as Bathocuproine (BCP) layer.
  • BCP Bathocuproine
  • Aluminum acts as the counter electrode.
  • the device Prior to characterization, the device is encapsulated via resin and the encapsulation glass acts as the top support.
  • the invention is based on the deposition of Pbl 2 by solution processing on the first region and the subsequent transformation of the Pbl 2 into the desired perovskite structure by applying/depositing vapor.
  • the reaction occurs within seconds and allows us to have much better control over the perovskite morphology compared to the previously employed routes.
  • the roughness of the perovskite film is limited by the roughness of Pbl 2 film because other precursors are applied in vapor form.
  • Another advantage of the method is that it is easily scalable to large area substrates. The use of this new procedure results not only in an excellent reproducibility of photovoltaic device performance, but also enabled us to reach a new record short circuit current density of 38 mA/cm to the best of our knowledge [Ren, Z. et al., Thermal assisted oxygen annealing for high efficiency planar 3 perovskite solar cells. Sci. Rep. DOI: 10.1038/srep06752].
  • Perovskite solar cells were fabricated on patterned indium tin oxide (ITO) glasses with a sheet resistance of 10 ⁇ /sq.
  • ITO indium tin oxide
  • the ITO glass was cleaned by sequential ultrasonic treatment in deionized water, acetone, and isopropanol (IPA), and then treated in a bench-top plasma cleaner (PE-50 bench top cleaner, The Plasma Etch, Inc., USA) for 2 min.
  • PE-50 bench top cleaner The Plasma Etch, Inc., USA
  • PEDOT:PSS Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate
  • PEDOT:PSS Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate
  • Pbl 2 is dissolved in ⁇ , ⁇ -dimethylformamide (DMF) with a concentration of 250 mg/mL.
  • DMF ⁇ , ⁇ -dimethylformamide
  • the Pbl 2 solution was spun on PEDOT:PSS coated substrate at 3,000 rpm for 20 s and then the resultant film was dried on a hot plate at 70 °C for 5 min and left for cooling.
  • the films are exposed to HI vapor (Merck, 67% in water) for 15 seconds and CH 3 NH 2 vapor (TCI, 40% in methanol) for 5 sec which is followed by another step of HI vapor for 30 seconds.
  • the films were annealed at 100 °C for 1 hour.
  • the PCBM solution (dissolved in ortho- dichlorobenzene with a concentration of 20 mg/mL) was spin coated on top of the perovskite layer at 1500 rpm for 35 s.
  • the substrate was annealed at 100 °C for 10 min.
  • the device was finished by evaporating Al (60 nm) in a base pressure of 2xl0 -6 mbar.
  • the device area was defined through a shadow mask from the overlap of the ITO and aluminum electrodes (10.9 mm 2 ).
  • the current density-voltage (J-V) measurement of the devices was conducted on a computer controlled Keithley 2602A source meter.
  • the J-V measurement system uses a solar simulator with a Class-A match to the AMI.5 Global Reference Spectrum. Film absorption spectra of the films were compared with a Shimadzu UV-2600 UV-Vis spectrophotometer. Atomic force microscopy (AFM) images of the samples were recorded on a ParkSystems XE-100E microscope. X-ray diffraction (XRD) measurements were performed with a Bruker D8 Discover X-ray diffractometer with copper K-a target X-ray tube. Film thickness measurements were determined with Ambios XP-200.
  • the surface roughness (R q ) of the film is mainly limited by the predeposited Pbl 2 film.
  • the R q value of the Pbl 2 film is 6.5 nm whereas R q value of the film is 8.5 nm.
  • perovskite films are also comparable as shown in Figure 5.
  • the typical thickness of perovskite films has been measured as 290 nm, slightly smaller than the optimum thickness of 300 nm [Momblona, C. et al., Efficient methylammonium lead iodide perovskite solar cells with active layers from 300 nm to 900 nm. Apl. Mat. 2014, 2, 081504].
  • crystal diffraction peaks indicate the perovskite formation is not complete and may explain the relatively poor fill factors of the devices obtained from these films compared to state of art.
  • the device performances can be optimized by increasing the conversion of Pbl 2 crystal to the 3 crystal.

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Abstract

La présente invention concerne un procédé de production de semi-conducteurs hybrides organiques-inorganiques à base de pérovskite. La présente invention permet de former des hétérojonctions planes avec une rugosité de film extrêmement faible, ce qui est important dans la fabrication de cellules solaires à haut rendement et d'autres dispositifs optoélectroniques. Le procédé permet de produire à grande échelle et à faible coût des cellules solaires à base de pérovskite, au moyen de systèmes industriels actuellement bien maîtrisés.
PCT/IB2015/055290 2015-07-13 2015-07-13 Procédé de production de films minces de pérovskite et dispositif optoélectronique Ceased WO2017009688A1 (fr)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107123739A (zh) * 2017-06-06 2017-09-01 华北电力大学 一种非铅铋基钙钛矿太阳电池光吸收层及其制备方法
RU2675610C1 (ru) * 2017-08-10 2018-12-20 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Способ получения пленки светопоглощающего материала с перовскитоподобной структурой
KR20190021135A (ko) * 2017-08-22 2019-03-05 엘지전자 주식회사 태양전지의 제조 방법
CN110323337A (zh) * 2019-06-26 2019-10-11 广西大学 一种铅锡二元钙钛矿光电探测器及其制备方法
RU2714273C1 (ru) * 2018-12-29 2020-02-13 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Способ формирования двухслойной светопоглощающей электропроводящей структуры
WO2020214994A1 (fr) * 2019-04-19 2020-10-22 Hunt Perovskite Technologies, L.L.C. Procédé de dépôt de pérovskite sans solvant
CN111933730A (zh) * 2020-08-20 2020-11-13 西安电子科技大学 基于无铅钙钛矿单晶的核辐射探测器及其制备方法
CN113193126A (zh) * 2021-04-08 2021-07-30 电子科技大学 一种实现无甲胺钙钛矿薄膜表面重构的制备方法及其应用
JP2022537253A (ja) * 2019-06-03 2022-08-25 メカロエナジー カンパニー リミテッド 化学気相蒸着法によるペロブスカイト太陽電池吸収層の製造方法
WO2022244412A1 (fr) * 2021-05-21 2022-11-24 パナソニックホールディングス株式会社 Cellule solaire et procédé de production associé
RU2795845C1 (ru) * 2022-07-12 2023-05-12 Федеральное Государственное Бюджетное Учреждение Науки Федеральный Исследовательский Центр Проблем Химической Физики И Медицинской Химии Российской Академии Наук (Фиц Пхф И Мх Ран) Способ получения фоточувствительных пленок Cu-Cr-Sn-S
US20230247853A1 (en) * 2022-01-28 2023-08-03 The Florida State University Research Foundation, Inc. Composite Materials, Devices, and Methods of Encapsulating Perovskites
CN118159108A (zh) * 2024-05-08 2024-06-07 北京大学 一种双异质结钙钛矿及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2846371A1 (fr) * 2013-09-10 2015-03-11 Ecole Polytechnique Fédérale de Lausanne (EPFL) Cellule solaire inversée et son procédé de fabrication
CN104409639A (zh) * 2014-11-03 2015-03-11 华东师范大学 一种有机钙钛矿薄膜的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2846371A1 (fr) * 2013-09-10 2015-03-11 Ecole Polytechnique Fédérale de Lausanne (EPFL) Cellule solaire inversée et son procédé de fabrication
CN104409639A (zh) * 2014-11-03 2015-03-11 华东师范大学 一种有机钙钛矿薄膜的制备方法

Non-Patent Citations (24)

* Cited by examiner, † Cited by third party
Title
BURSCHKA, J. ET AL.: "Sequential deposition as a route to high-performance perovskite-sensitized solar cells", NATURE, vol. 499, 2013, pages 316 - 319
CAI, B.; XING, Y.; YANG, Z.; ZHANG, W.-H.; QIU, J.: "High performance hybrid solar cells sensitized by organolead halide perovskites", ENERGY ENVIRON. SCI., vol. 6, 2013, pages 1480 - 1485
CHEN, Q. ET AL.: "Planar heterojunction perovskite solar cells via vapor-assisted solution process", J. AM. CHERN. SOC., vol. 136, 2014, pages 622 - 625
CROSSLAND, E. J. W. ET AL.: "Mesoporous Ti02 single crystals delivering enhanced mobility and optoelectronic device performance", NATURE, vol. 495, 2013, pages 215 - 219
EDRI, E.; KIRMAYER, S.; CAHEN, D.; HODES, G.: "High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite", PHYS. CHERN. LETT., vol. 4, 2013, pages 897 - 902
ETGAR, L. ET AL.: "Mesoscopic CH NH PbI /Ti0 heterojunction solar cells", J AM. CHERN. SOC., vol. 134, 2012, pages 17396 - 17399
HAO, F. ET AL.: "Controllable perovskite crystallization at a gas-solid interface for hole conductor-free solar cells with steady power conversion efficiency over 10%", J. AM. CHERN. SOC., vol. 136, 2014, pages 16411 - 16419
IM, J.-H. ET AL.: "6.5% efficient perovskite quantum-dot-sensitized solar cell", NANOSCALE, vol. 3, 2011, pages 4088 - 4093
IM, J.-H. ET AL.: "Growth of CH NH Pbl cuboids with controlled size for high-efficiency perovskite solar cells", NATURE NANOTECHNOLOGY, vol. 9, 2014, pages 927 - 932
IM, J.-H.; CHUNG, J.; KIM, S.-J.; PARK, N.-G.: "Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH CH NH )PbI", NANOSCALE RES. LETT., vol. 7, 2012, pages 353
KIM, H.-S. ET AL.: "Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%", SCI. REP., vol. 2, 2012, pages 591
KOJIMA, A.; TESHIMA, K.; SHIRAI, Y.; MIYASAKA, T.: "Organometal halide perovskites as visible-light sensitizers for photovoltaic cells", J. AM. CHERN. SOC., vol. 131, 2009, pages 6050 - 6051
LEE, M. M.; TEUSCHER, J.; MIYASAKA, T.;; MURAKAMI, T. N.; SNAITH, H. J.: "Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites", SCIENCE, vol. 338, 2012, pages 643 - 647
LIU, M.; JOHNSTON M. B.;; SNAITH, H. J.: "Efficient planar heterojunction perovskite solar cells by vapour deposition", NATURE, vol. 501, 2013, pages 395 - 398
MINGZHEN LIU ET AL: "Efficient planar heterojunction perovskite solar cells by vapour deposition", NATURE, vol. 501, no. 7467, 11 September 2013 (2013-09-11), pages 395 - 398, XP055097500, ISSN: 0028-0836, DOI: 10.1038/nature12509 *
MITZI D. B. ET AL.: "Organic-inorganic electronics", IBM JOURNAL OF RESEARCH AND DEVELOPMENT, vol. 45, 2001, pages 29 - 45
MITZI, D. B. ET AL.: "Conducting layered organic-inorganic halides containing 110 -oriented perovskite sheets", SCIENCE, vol. 267, 1995, pages 1473 - 1476
MOMBLONA, C. ET AL.: "Efficient methylammonium lead iodide perovskite solar cells with active layers from 300 nm to 900 nm", APL. MAT., vol. 2, 2014, pages 081504
NAM-GYU PARK: "Perovskite solar cells: an emerging photovoltaic technology", MATERIALS TODAY, vol. 18, no. 2, 1 March 2015 (2015-03-01), pages 65 - 72, XP055200828, ISSN: 1369-7021, DOI: 10.1016/j.mattod.2014.07.007 *
NOH, J. H.; IM, S. H.;; HEO, J. H.; MANDAI, T. N.; SEOK, S. I.: "Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells", NANO LETT., vol. 13, 2013, pages 1764 - 1769
QUI, J. ET AL.: "All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional Ti02 nanowire arrays", NANOSCALE, vol. 5, 2013, pages 3245 - 3248
WANG QIONG ET AL: "Control of organic-inorganic halide perovskites in solid-state solar cells: a perspective", SCIENCE BULLETIN, SCIENCE CHINA PRESS, HEIDELBERG, vol. 60, no. 4, 4 February 2015 (2015-02-04), pages 405 - 418, XP035448479, ISSN: 2095-9273, [retrieved on 20150204], DOI: 10.1007/S11434-015-0734-Y *
WEI E. I. SHA ET AL: "The efficiency limit of CH3NH3PbI3 perovskite solar cells", APPLIED PHYSICS LETTERS, vol. 106, no. 22, 1 June 2015 (2015-06-01), 2 Huntington Quadrangle, Melville, NY 11747, pages 221104, XP055232586, ISSN: 0003-6951, DOI: 10.1063/1.4922150 *
XIAO, Z. ET AL.: "Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers", ENERGY ENVIRON. SCI., vol. 7, 2014, pages 2619

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