WO2019195873A1 - Procédé de formation d'une pérovskite - Google Patents

Procédé de formation d'une pérovskite Download PDF

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Publication number
WO2019195873A1
WO2019195873A1 PCT/AU2018/051016 AU2018051016W WO2019195873A1 WO 2019195873 A1 WO2019195873 A1 WO 2019195873A1 AU 2018051016 W AU2018051016 W AU 2018051016W WO 2019195873 A1 WO2019195873 A1 WO 2019195873A1
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perovskite
salt
metal
dopant
component
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PCT/AU2018/051016
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English (en)
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Anita Wing Yi Ho-Baillie
Shujuan HUANG
Meng Zhang
Cho Fai Jonathan LAU
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Newsouth Innovations Pty Limited
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Priority claimed from AU2018901203A external-priority patent/AU2018901203A0/en
Application filed by Newsouth Innovations Pty Limited filed Critical Newsouth Innovations Pty Limited
Publication of WO2019195873A1 publication Critical patent/WO2019195873A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
    • H—ELECTRICITY
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    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868—Passivation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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    • 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 invention relates to a method of forming a perovskite and photovoltaic elements comprising
  • a first aspect of the invention provides a method of forming a perovskite having a formula of ABX3, comprising: providing a film of precursor solution for forming the perovskite, the solution comprising a first salt for forming component A, and a mixture of a second salt and a dopant salt for forming component B, wherein component X is formed from anions of the salts; and
  • a molar ratio of [the second salt] : [the dopant salt] in the precursor solution is such that the perovskite has a surface enriched with the metal of the dopant salt compared to a bulk of the perovskite.
  • metal of the dopant salt refers to the element that is formed from the dopant/first/second salt is no longer in free in solution in its ionic form and instead is incorporated into the perovskite in a crystal lattice and/or in its metallic (i.e. M°) form.
  • the molar ratio of [the second salt] : [the dopant salt] in the precursor solution may range from about 99:1 to about 85:15.
  • a molar ratio of [a metal of the second salt] : [the metal of the dopant salt] at the surface may range from about 95:5 to about 30:70.
  • the second salt may be a divalent species .
  • the second salt is a Pb 2+ .
  • the second salt may be Sn 2+ .
  • the dopant salt may include a salt of a group 2 element, or any salt having the properties of a group 2 salt, or a bivalent (divalent) salt.
  • the dopant salt can include Mg 2+ , Ba 2+ , Sr 2+ , Ca 2+ , Zn 2+ , Mn 2+ , Co 2+ , Ge 2+ , Pd 2+ and/or Sn 2+ .
  • a salt having the properties of a group 2 salt may include a salt having a similar atomic radii of a group 2 metal salt, such as Sn 2+ .
  • a combination of dopant salts may be used.
  • the dopant salt is a trivalent species .
  • a molar ratio of [Pb 2+ ] : [Sr 2+ ] in the precursor solution ranges from about 99:1 to about 95:5, or a molar ratio of [Pb 2+ ] : [Ca 2+ ] in the precursor solution ranges from about 98:2 to 85:15. In an embodiment, a molar ratio of [Pb 2+ ] : [Sr 2+ ] in the precursor solution is 98:2. In an embodiment, a molar ratio of [Pb 2+ ] : [Ca 2+ ] in the precursor solution is 95:5.
  • the first salt may include a salt from a group 1 element or any salt having the properties of a group 1 salt or a monovalent ion.
  • the first salt may include Ag + , Rb + , K + and/or Cs + .
  • the first salt includes an organic compound.
  • the monovalent ion may be the organic compound.
  • the organic compound may be a methylammonium ion.
  • the anions of the salts may include Cl- , F-, I- and/or Br- .
  • the precursor solution may comprise a single solvent.
  • the solvent may be a polar organic solvent, such as N- Methyl-2-pyrrolidone (NMP) , dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) .
  • the solvent may comprise a solvent mixture of polar organic solvents .
  • the precursor solution may comprises a mixture of DMF: DMSO. The mixture may range from about 99:1 to about 1:99 v/v DMF: DMSO.
  • the precursor solution may comprise a mixture of about 2:1 v/v to 4:1 v/v DMF: DMSO.
  • a DMF: NMP solvent mixture is used as the precursor solution.
  • the method may further comprise forming the film of precursor solution on a substrate.
  • the precursor solution may be formed via spin coating.
  • the film of the precursor solution may be heated to a temperature ranging from about 100°C to about 300°C. This can help to release excess solvent and form the perovskite.
  • the dopant is Sr 2+
  • the film of the precursor solution may be heated to 100°C.
  • the dopant is Ca 2+
  • the film of the precursor solution may be heated to 300°C .
  • a second aspect provides a perovskite formed using the method of the first aspect.
  • a third aspect provides a perovskite having a formula of ABX3 for use in a photovoltaic element, comprising: a first component as component A, a mixture of a second metal and a dopant metal as component B, and one or more halides as component X;
  • a surface of the perovskite is enriched with the dopant metal compared to a bulk of the perovskite .
  • the dopant metal may be in its oxide form at the surface.
  • a molar ratio of [the second metal] : [the dopant metal] at the surface may range from about 95:5 to about 30:70.
  • a molar ratio of [the second metal] : [the dopant metal] in the bulk of the perovskite may range from about 96:4 to about 85:15.
  • the first component metal may be a metal including a group 1 element, or an element capable of having the properties of a group 1 element, or an element capable for forming a monovalent ion, or an organic compound, such as Ag, Rb, K, Cs and/or a methylammonium species.
  • the dopant metal may include a group 2 element or any element having group 2 properties or a metal capable of forming a bivalent (divalent) ion, including Sn, Mg, Ba,
  • the one or more halides may include F, Cl, I and/or
  • the second metal may be Pb.
  • a formula of the perovskite may be CsPbi-xSrxl2Br or CsPbi-xCaxl3.
  • a formulate of the perovskite may be MAPbi- xYxl3, where MA is a methylammonium species and Y is Ca or
  • a forth aspect provides a photovoltaic device
  • a fifth aspect provides a photovoltaic element comprising :
  • a first layer comprising a perovskite having a formulate ABX3, wherein component A comprises a first component, component B comprises a mixture of a second metal and a dopant metal, and component X comprises one or more halides;
  • a surface of the perovskite is enriched with the dopant metal compared to a bulk of the perovskite .
  • the perovskite may be otherwise as defined according to the third aspect.
  • the surface may be enriched with the dopant metal . Some of the dopant metal present at the surface may be in its oxide form.
  • the surface enriched by the dopant metal may be configured to provide a
  • the photovoltaic element may further comprise an anti-reflective layer.
  • the anti-reflective layer may be MgF2.
  • the photovoltaic element may have a PCE ranging from about 10% to about 13.5%.
  • a sixth aspect provides a method of forming a photovoltaic device, comprising:
  • the first solar cell structure comprising a perovskite having a formulate ABX3, wherein
  • component A comprises a first component
  • component B comprises a mixture of a second metal and a dopant metal
  • component X comprises one or more halides; wherein a surface of the perovskite is enriched with the dopant metal compared to a bulk of the perovskite.
  • Depositing the first layer may comprises the method of the first aspect.
  • Figure 1 shows X-ray diffraction patterns
  • perovskite films made from different CsPbi- xC a xl 3 precursors where x is the molar ratio of Ca 2+ in the precursor solution.
  • x is the molar ratio of Ca 2+ in the precursor solution.
  • * in Figure 1 denotes Pbl2 impurity peak and # denotes FTO peak.
  • Figure 2 shows scanning electron microscopy images of CsPbi- xC a xl 3 perovskite films where x is the molar ratio of Ca 2+ in the precursor solution (a) CsPbl3, (b)
  • Figure 3 shows 3-dimensional atomic force microscopy (AFM) images of the implied CsPbi- x Ca x l 3 perovskite films where x is the molar ratio of Ca 2+ in the precursor solution (a) CsPbl3, (b) CsPbo. 9 sCao.02I 3 , (c) CsPbo. 95 Cao.05I 3 , and (d) CsPbo. 93 Cao.07I 3 .
  • AFM atomic force microscopy
  • Figure 4 shows size distributions of complexes in CsPbi- xC a xl 3 perovskite precursor solution obtained from dynamic light scattering (DLS) measurements where x is the molar ratio of Ca 2+ in the precursor solution.
  • DLS dynamic light scattering
  • Figure 5 shows XPS spectra of (a) Ca 2p, (b) Pb 4f,
  • FIG. 6 shows (a) absorbance spectra and (b) time- resolved PL (tr-PL) decays of perovskite films fabricated using CsPbi- x Ca x l3 precursor solutions.
  • Figure 7 shows photovoltaic parameters (with standard deviations) of perovskite devices as a function of Ca 2+ substitution in the perovskite precursor solution.
  • Figure 8 shows (a) light J-V characteristics under reverse scan and (b) EQE spectra of champion CsPbi- x Ca x l3 devices where x is the molar ratio in the precursor, (c) Light J-V characteristics under reverse scan of the champion device using 5% Ca 2+ in precursor before and after MgF2 anti-reflection layer, (d) Stabilised output measured at the maximum power point (0.8V) for the best performing device with MgF2.
  • Figure 9 Cross-sectional SEM image of a typical device structure FT0/c-Ti0 2 /mp-Ti0 2 /CsPbl 3 /P3HT/Au; Scale Bar is 500 nm.
  • perovskite films fabricated using CsPbi- x Ca x l3 precursor solution .
  • Figure 14 Distributions of reverse scan PCE of 26 perovskite devices fabricated using 5% Ca 2+ substitution in the precursor solution.
  • Figure 17 Relative humidity of ambient in which perovskite devices were stored.
  • Figure 18 shows (a) XRD patterns of CsPblABr films and (b) light J-V characteristics of CsPbI2Br devices using different annealing temperature.
  • Figure 19 shows (a) XRD patterns of low-temperature- processed CsPbi- x Sr x l2Br films and SEM images of (b)
  • Figure 20 shows XPS spectra for (a) Pb 4f and Sr 3d and (b) I 3d for the CsPbi- x Sr x l2Br films.
  • Figure 21 shows (a) absorbance spectra and (b) time- resolved PL (tr-PL) decay profiles of CsPbi- x Sr x l2Br films.
  • Figure 22 shows (a) light J-V characteristics under reverse scan and (b) EQE spectra and (c) photovoltaic parameters (with standard deviations) of FT0/c-Ti0 2 /mp- Ti0 2 /CsPbi- x Sr x l 2 Br/P3HT/Au devices as a function of Sr 2+ concentration in the perovskite.
  • Figure 23 shows (a) light J-V characteristics and electrical parameters under different scan conditions (red: 0.1 V/s; black: 1 V/s) for the CsPbo.9sSro.o2l2Br champion device, (b) photocurrent density (black) and PCE (red) as a function of time for the champion
  • CsPbo.98Sro .02l2Br (initial efficiency: 9.5%) perovskite solar cell as a function of storage time, and (d) light J-V characteristics of CsPbo.9sSro.o2l2Br (black) and CsPblhBr (red) cells before and after heat treatment at 100 °C for lh. Solid line: before heat treatment; dashed line: after heat treatment .
  • Figure 24 shows photovoltaic parameters under reverse scan of FT0/c-Ti0 2 /mp-Ti0 2 /CsPbl 2 Br/P3HT/Au devices at two annealing temperatures.
  • Figure 25 shows SEM top view images of CsPblhBr films annealed at (a) 100 °C and (b) 310 °C. Scale bar is 2pm.
  • Figure 26 shows XRD patterns of CsPbi- xS r xl 2Br films annealed at 310 °C for 10 minutes.
  • Figure 27 shows top view SEM image of CsPbo.9sSro.o2l2Br film and the corresponding energy dispersive spectroscopy (EDS) elemental mapping of Cs (red) , Pb (blue) , Sr
  • EDS energy dispersive spectroscopy
  • Figure 28 shows SEM images of (a) CsPbo. ggSro.oil2Br, (c) CsPbo.97Sro .03l2Br films and corresponding SEM images under backscattered mode of the same (b) CsPbo. ggS ro.oil2Br (d)
  • Figure 29 shows XPS spectra of CsPbi- xS r xl 2Br films for Sr3p at the surface (black curve) and at 10 nm depth (red curve) .
  • the peak shift from 269.5 eV (lOnm depth) to 268.5 eV at the surface indicates Sr oxide might have formed on the surface.
  • Figure 30 shows steady-state PL spectra of CsPbi- x Sr x l2Br films.
  • Figure 31 shows distributions of reverse scan PCE of 25 CsPbo.98Sro.o2l2Br devices fabricated in this work.
  • Figure 32 shows normalized Jsc, Voc, FF, and PCE for CsPb ⁇ 2Br perovskite solar cells with encapsulation as a function of storage time (initial efficiency is 6.2 %).
  • a first aspect of the invention provides a method of forming a perovskite having a formula of ABX3, comprising:
  • a precursor solution comprising a first salt for component A, and a mixture of a second salt and a dopant salt for component B, wherein anions of the salts provides component X;
  • a molar ratio of [the second salt] : [the dopant salt] in the precursor solution is such that the perovskite has a surface enriched with a metal of the dopant salt compared to a bulk of the perovskite.
  • a passivation layer at the surface of the perovskite may be formed.
  • the passivation layer may help to prevent carrier recombination and improve the efficiency of the photovoltaic element.
  • the metal of the dopant salt is in its oxide form at the surface.
  • CaO may be present as the oxide at the surface of the perovskite.
  • the oxide layer may be formed by reaction of the dopant salt in the precursor solution during synthesis of the perovskite.
  • the oxide layer may also be formed by reaction of the metal of the dopant salt reacting with oxygen at the surface of the perovskite .
  • the concentration of the dopant may range from about 99:1 to about 85:15.
  • the ratio of [the second salt] : [the dopant salt] can vary depending on the dopant salt. In some embodiments more than one dopant salt can be used, where the total concentration of the dopant salts is used to determine the ratio of [the second salt] : [the dopant salt] .
  • the molar ratio of [a metal of the second salt] : [the metal of the dopant salt] at the surface will differ from the ratio of [the second salt] : [the dopant salt] used in the precursor solution.
  • the molar ratio of [a metal of the second salt] : [the metal of the dopant salt] at the surface ranges from about 95:5 to about 30:70. Again, the specific ratio will be
  • the second salt determined by the second salt and the types of dopant salts, their relative ratios, and the perovskite to be formed .
  • the dopant salt may include a salt of a group 2 element or any salt having the properties of a metal salt from a group 2 element or a bivalent salt.
  • the dopant salt may include Mg 2+ , Ba 2+ Ca 2+ Zn 2+ , Mn 2+ , Co 2+ , Ge 2+ , Pd 2+ , Sn 2+ , and/or Eu 2+ .
  • a combination of one or more dopant salts may be used.
  • a valency of the dopant salt may be selected to be the same as a valency of the second salt.
  • the second salt may be Sn 2+ or Pb 2+ .
  • a dopant salt into the perovskite, the amount of e.g. Pb required to form the perovskite can be reduce. This can be advantageous since reducing the amount of Pb helps to reduce the environmental impacts associate with forming, using, and disposing the perovskite.
  • Sr 2+ or Ca 2+ is used as the dopant salt.
  • a molar ratio of [Pb 2+ ] : [Sr 2+ ] in the precursor solution may range from about 99:1 to about 95:5.
  • a molar ratio of [Pb 2+ ] : [Ca 2+ ] in the precursor solution may range from about 98:2 to 85:15. Molar ratios outside of the 99:1 to about 95:5 for
  • [Pb 2+ ] : [Sr 2+ ] and 98:2 to 85:15 for [Pb 2+ ] : [Ca 2+ ] tend to form perovskites with little to no enriched surface or a surface that becomes too insulating.
  • surface enrichment with the metal of the dopant salt occurs due to kinetic and thermodynamic effects during perovskite formation, with the perovskite trying to achieve its lowest energy state. Because surface enrichment occurs in situ during formation of the perovskite, may be no need for further surface modification to provide favourably perovskite surface properties. Put another way, the perovskite may self- assemble to form the surface passivation layer.
  • a molar ratio of [Pb 2+ ] : [Sr 2+ ] in the precursor solution is 98:2. In an embodiment, a molar ratio of [Pb 2+ ] : [Ca 2+ ] in the precursor solution is 95:5.
  • the first salt may include a salt from a group 1 element or any salt having the properties of a metal salt from a group 1 element or a monovalent ion.
  • the first salt may include Ag + , Rb + , K + , Cs + and/or a methylammonium ion.
  • a mixture of salts may be used as the first salt. Changing the first salt may help to improve the stability of the perovskite when heating, for example when annealing.
  • Changing the first salt may help to reduce the annealing temperature ( s ) required to form the perovskite.
  • Cs + may be advantageous in some embodiments as it can reduce the annealing temperature to around 100° when Sr 2+ is used as the dopant salt.
  • the annealing temperature may be about 300°C when Cs + is used as the first salt and Ca 2+ is used as the dopant salt.
  • the perovskite can be considered an inorganic perovskite.
  • a methylammonium salt or similar may be used as the first component.
  • the perovskite can be considered an organic perovskite.
  • the disclosure is to be interpreted broadly to include both inorganic and organic perovskites unless context clearly indicates otherwise.
  • the anions of the salts may include Cl-, F-, I- and/or Br- .
  • the precursor solution may be a solvent or a solvent mixture having two or more solvents.
  • the precursor solution comprises a mixture of DMF:DMSO.
  • Some embodiment use a mixture of DMF:NMP as the solvent for the precursor solution.
  • the mixture may range from about 2:1 v/v to 4:1 v/v DMF:DMSO.
  • a 4:1 DMF:NMP v/v mixture is used.
  • the specific ratio of DMF:DMSO and/or DMF:NMP may be determined by the first, second and dopant salts used to form the perovskite.
  • the solubility of one of the salts in the precursor solution may determine the type(s) of solvent used.
  • the method may further comprise applying the
  • the substrate may be a substrate used to form a photovoltaic cell.
  • the substrate may be mp-Ti0 2 .
  • the precursor solution may be applied to the substrate via spin coating. Once applied to the substrate, the precursor solution would then be heated (e.g. annealed) to form the perovskite. Heating may help to accelerate evaporation of the solvent (s) used to form the perovskite.
  • the presence of the dopant salt may help to reduce colloidal cluster size during the heating step, and this may help to improve film smoothness. This may be
  • a second aspect provides a perovskite formed using an embodiment of the method as set forth above.
  • a third aspect provides a perovskite having a formula of ABX 3 for use in a photovoltaic element, comprising:
  • a first component for component A a mixture of a second metal and a dopant metal for component B, and one or more halides for component X;
  • a surface of the perovskite is enriched with the dopant metal compared to a bulk of the perovskite .
  • the dopant metal may be in its oxide form at the surface.
  • the surface of the perovskite may comprise CaO or SrO, respectively. It should be appreciated that not all of the dopant metal at the surface will be in its oxide form, so the surface can comprise a mixture of the dopant metal in its oxide form and other forms.
  • the composition and ratio of the metals that form the perovskite will vary between the surface and a bulk of the perovskite.
  • a molar ratio of [the second metal] : [the dopant metal] at the surface ranges from about 95:5 to about 30:70, but a molar ratio of [the second metal] : [the dopant metal] in the bulk of the perovskite ranges from about 96:4 to about 85:15.
  • the specific ratios and relative difference in composition between the surface and the bulk will be determined by the first, second and dopant metals and their relative molar ratios to one another .
  • the first component may include a metal from a group 1 element or any element having group 1 properties and/or any element that is capable of being incorporated into a perovskite structure in the position of a group 1 element.
  • the first component may include Ag, Rb, K and/or Cs .
  • an element having a similar atomic radii of a group 1 element may be used as the first metal so long as it can be incorporated into the perovskite structure in the same position as a group 1 element such as Cs .
  • a mixture of metals may be used as the first metal.
  • the first component is an organic component such as a methylammonium species.
  • a mixture of organic component (s) and metal (s) can be used in some embodiments.
  • the dopant metal may include a group 2 element, any element having group 2 properties, and/or any element that is capable of being incorporated into a perovskite structure in the position of a group 2 element.
  • the dopant metal may be Mg, Ca, Sr, Ba, Zn, Mn, Co, Ge , Pd , S n and/or Eu.
  • the one or more halides may include F, Cl, I and/or Br .
  • the second metal may be Pb. Incorporating the dopant metal helps to reduce the amount of Pb in the perovskite and this can be advantageous as it helps to reduce the environmental impacts of the perovskite, its use and subsequent disposal.
  • a formula of the perovskite is CsPbi-xSrx ⁇ 2Br or CsPbi-xCaxl 3 .
  • a formulate of the perovskite may also include MAPbi-xYx ⁇ 3, where Y is the dopant metal and MA is a methylammonium species .
  • Another embodiment provides a photovoltaic element comprising an embodiment of a perovskite as defined above.
  • a first layer comprising a perovskite having a formulate ABX3, wherein component A comprises a first component, component B comprises a mixture of a second metal and a dopant metal, and component X comprises one or more halides;
  • a surface of the perovskite is enriched with the dopant metal compared to a bulk of the perovskite .
  • the perovskite may be otherwise as defined as set forth above.
  • the surface may be enriched with the dopant metal.
  • the dopant metal may be in its oxide form at the surface .
  • the surface enriched by the dopant metal may be configured to provide a passivating effect for the first layer. Put another way, the surface enriched by the dopant metal may act as a passivation layer.
  • a passivation layer can help to reduce the occurrence of recombination which can help to improve the efficiency of the photovoltaic element.
  • the photovoltaic element may further comprise an anti-reflective layer.
  • the anti-reflective layer may be MgF2.
  • the anti-reflective layer may help to improve the efficiency of the photovoltaic element.
  • the photovoltaic element may have a PCE ranging from about 10% to about 13.5%.
  • the photovoltaic element may be used in a
  • multilayer photovoltaic cell such as a tandem cell.
  • TEC10, 10 QD-l was cleaned by sonication in deionized water with 2 % Hellmanex, acetone and isopropanol for 20 min, respectively. After drying, the substrate was treated by UV ozone cleaner for 20 min.
  • c-Ti0 2 a solution of titanium
  • the substrate was dried at 100°C for 10 min and then annealed at 450 °C for 30 min. Prior to deposition of perovskite film, the substrate was cleaned by a UVO cleaner for another 20 min and was then
  • the Csl concentration in the CsPbi- xC a xl 3 perovskite precursor solution is 1 M, which was prepared by dissolving Csl (Alfa Aesar) , Pbl2 (Alfa Aesar) and Cal2 (Sigma-Aldrich) , stoichiometrically in a mixed solvent of dimethylformamide (DMF) (Sigma- Aldrich) and DMSO (Sigma-Aldrich) with a volume ratio of 4:1.
  • the perovskite film was deposited by gas-quenching method (gas assisted spin coating) .
  • the substrate was spun firstly at 1000 rpm for 10 s and then 4000 rpm for 30 s.
  • N2 stream (5.5 bar) was blown over the spinning substrate for 15 s after spinning at 4000 rpm for 5 s.
  • the perovskite film was then annealed at 300 °C for 10 min on a hot plate.
  • the hole transporting solution was prepared by dissolving 10 mg/ml Poly ( 3-hexylthiophene ) (P3HT) (Sigma-Aldrich) in chlorobenzene (Sigma Aldrich) and was deposited on perovskite layer by spin coating at 3000 rpm for 30 s.
  • the silicone elastomer base and its curing agent (Sylgard 184) were purchased from Dow Corning.
  • Sylgard 184 The silicone elastomer base and its curing agent
  • the reagents were mixed at a ratio 10:1 (w/w) and degassed for about an hour to prepare the cross-linking silicone elastomer which were then poured onto the perovskite film. After curing for 1 day, the implied perovskite films were obtained by peeling the silicone gel off the perovskite surface .
  • XRD X-ray diffraction
  • X-ray photoelectron spectroscopy (XPS) study was carried using the Thermo ESCALAB250Xi X-ray photoelectron spectrometer. The optical reflection and transmission spectra were measured using Cary spectrophotometer and the test samples are
  • time-resolve PL (tr-PL) decay traces were measured by the Microtime-200 (PicoQuant) with 470 nm excitation and detection through a 620/40 nm band pass filter.
  • X-ray diffraction (XRD) measurements were carried out on FT0/c-Ti0 2 /mp-Ti0 2 /CsPbi- xC a xl3 test structures where x is the molar ratio of Ca in the precursor.
  • Figure 1 shows the XRD patterns of the CsPbi- x Ca x l3 films . They all show typical cubic perovskite phase with the main XRD peaks at 14.5°, 20.8°, and 29.1° corresponding to (100), (110) and
  • the reference CsPbl3 film (0% Ca) has a small peak at 12.6° corresponding to a Pbl2 which is typical when there is an incomplete conversion of the precursor into perovskite phase.
  • the Pbl2 peak disappears and the crystallinity of perovskite phase improves.
  • XRD peaks were expected to lower 2 theta angle when Pb is partially substituted with alkaline-earth metal such as Mg, Sr, Ba and Ca .
  • alkaline-earth metal such as Mg, Sr, Ba and Ca
  • the size of the colloids can be determined from the DLS measurements and results for solutions with different molar ratios of Ca 2+ are shown in Figure 4. It can be seen that the radius of the colloids in the reference sample (0% Ca) is predominantly 1.7 pm. As the molar ratio of Ca increases, the colloidal particle size is reduced to 1 pm. This could be due to the Ca 2+ being a hard Lewis acid similar to hydrogen, H + , compared to Pb 2+ , which is a soft acid, according to the Lewis acidity. The Ca 2+ might work similarly to hydrohalic acids, triggering the dissolution of the colloids in the precursor solution reducing the size of the colloids. The smaller colloid results in a more uniform distribution of the reactants inducing better nucleation and crystallization of the
  • CaO could be a result of reaction between Ca 2+ and H2O in dimethylformamide (DMF)
  • the CaC03 is the result of reaction between CaO and CO2 likely to be from the ambient.
  • DMF dimethylformamide
  • the XRD peaks of CaC03 are located at similar positions to the peaks of CsPbl3, it is hard to distinguish it in the XRD patterns .
  • the wider bandgap materials such as CaO ( ⁇ 6.3eV) or CaC03 (7eV) at the surface, recombination is suppressed similar to the passivation effect provide by excess Pbl2 in perovskite.
  • excessive amount of Ca 2+ is detrimental to device performance due to the insulating nature of this oxide layer, which will be discussed later.
  • the Ca atomic ratio is around 5%, slightly lower than 7% as anticipated (Table 2) .
  • the Ca ratio is 7%, again slight lower than the expected 10%. This suggests that the film 50nm into the bulk has slightly less Ca 2+ than that in the precursor solution, due to the accumulation of Ca 2+ at the surface as shown in previous results.
  • Figure 6b shows the tr-PL decay curves for the perovskite films and Table 3 shows the corresponding carrier lifetime components extracted by fitting the curves with a bi-exponential function. Table 3. Lifetimes extracted from tr-PL decay curves for perovskite films deposited using CsPbl-xCaxI3 precursor solutions .
  • Perovskite films made from precursors with 5% and 7% Ca 2+ substitution have better effective lifetimes compared to that of the reference CsPbl3 due to the improved film morphology including coverage and smoothness as shown in Figures 2 and 3 and effective passivation provided by the Ca rich oxide layer at the surface.
  • the precursor e.g. molar ratio at 2%
  • poorer coverage of the film Figure 2b
  • rougher surface Figure 3b and Table 1 .
  • Figure 15 shows light J-V characteristics of champion Cs perovskite devices using CsPbo.98Cao.02I3
  • the PCE of the champion cell was 13.5% with a JSC of 17.9 mAcrrr 2 ,
  • the perovskite film made from 5% Ca 2+ substitution in precursor has a lower Pb content and a bandgap of 1.72 eV. The latter makes it as a good candidate as a top cell in a double junction perovs kite/Si tandem device.
  • TEC10 10 W III-l
  • TEC10 10 W III-l
  • deionized water 2% Hellmanex, acetone, and isopropanol
  • UV ozone cleaner 20 min.
  • a solution of titanium diisopropoxide bis- (acetylacetonate ) in ethanol was deposited on the clean substrates by spray pyrolysis at 450 °C, and the substrate5 was subsequently annealed on a hot plate at 400 °C.
  • a 150 nm mp-Ti0 2 layer was deposited by spin coating for 12 s for 4000 rpm, using a Dyesol 30 NR-T paste with a 1:6 (by weight) dilution in ethanol. After spin coating, the substrate was dried at 100 °C for 10 min and then annealed at 450 °C for 30 min. Prior to
  • the substrates were cleaned by a UVO cleaner for another 20 min and were then transferred to a N2-filled glovebox.
  • the CsBr
  • concentration in the perovskite precursor solution is 0.7 M, which were prepared by dissolving CsBr (Alfa Aesar) ,
  • the perovskite film was deposited by a gas-quenching method (gas assisted spin coating) . After the perovskite precursor solution was spread on the mesoporous Ti02 layer, the substrate was spun first at 1000 rpm for 10 s and then at 4000 rpm for 30 s. A N2 stream (5.5 bar) was blown over the spinning substrate for 15 s after spinning at 4000 rpm for 5 s. The perovskite film was then annealed at 100 °C for 5 min on a hot plate.
  • the hole transporting precursor solution was prepared by dissolving 10 mg/mL poly (3- hexylthiophene ) (P3HT) (Sigma-Aldrich) in chlorobenzene (Sigma-Aldrich) and was deposited on the perovskite by spin coating at 3000 rpm for 30 s. Gold (100 nm) was then thermally evaporated on the HTM to form the top electrode. Finally, the device was encapsulated using polyisobutene (PIB) .
  • P3HT poly (3- hexylthiophene )
  • chlorobenzene Sigma-Aldrich
  • Top-view and cross-sectional SEM images were obtained using a field emission SEM (NanoSEM 230) in vacuum. EDS measurements were carried out by the NanoSEM 230 using a Bruker SDD-EDS detector in vacuum.
  • the sample used for XRD measurement was ( FTO/CsPbi- xS r xl 2Br/poly (methyl methacrylate)). Poly (methyl methacrylate (PMMA) was coated on the film to seal the sample from ambient moisture.
  • the optical reflection and transmission spectra were measured using a Cary spectrophotometer, and the test samples were encapsulated.
  • CsPbl2Br thin films are obtained by dissolving CsBr and Pbl2 stoichiometrically in a mixed solvent of N,N- dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) . Films are spin-coated and then annealed at 100 or 310 °C on a hot plate to form a 250 nm thick perovskite film.
  • CsPb ⁇ 2Br annealed at low temperature has a broader fwhm than the film annealed at high temperature. This indicates that the crystal size of the low temperature- processed CsPb ⁇ 2Br is smaller than that from the high-temperature-processed sample.
  • the top-view scanning electron microscopy (SEM) in Figure 24 shows that the crystal size of the low- temperature-processed CsPbl2Br film is around 200-500 nm, while the crystal size of the high-temperature processed CsPb ⁇ 2Br film is around 1-2 pm.
  • Solar cells annealed at these low and high temperatures are then fabricated with the structure of FT0/compact-Ti0 2 ( c-Ti0 2 ) /mesoporous- Ti0 2 (mp-Ti0 2 ) /CsPblhBr/poly ( 3-hexylthiophene-2 , 5-diyl ) (P3HT)/Au.
  • P3HT is chosen because of better stability compared to the commonly used spiro-OMeTAD .
  • the light current density versus voltage (J-V) characteristics under 1 sun illumination of these devices are shown in Figure 18b.
  • the best device that uses a low-temperature-processed CsPb ⁇ 2Br has a higher PCE (>7%) than the best device that uses a high-temperature-processed CsPblABr (the
  • perovskite is altered. However, it is hard to discern change in the perovskite peak location due to the reduced peak intensity and the similar ionic radius of Sr (118 pm) and Pb (119 pm) .
  • the XRD patterns of high-temperature- processed CsPbi- xS r xl 2Br films are also measured (see Figure 25) . Identical peaks can be observed. In terms of
  • FIG. 26 shows XRD patterns of CsPbi- xS r xl 2Br films annealed at 310 °C for 10 minutes.
  • Figure 26 shows that the XRD patterns of the CsPbi- xS r xl 2Br films annealed at high temperature have basically the same pattern as films annealed at low temperature. The difference between the red and black lines is quite similar to that observed in films annealed at low
  • Figure 19b-f shows the top-view SEM of the CsPbl2Br film and films with increasing Sr content.
  • the reference CsPbl2Br film shows a rough surface and is composed of densely packed crystalline grains, with an average grain size of ⁇ 200-500 nm.
  • the addition of Sr 2+ drastically changes the morphology of the perovskite and results in the appearance of "snowflakes", which appear brighter under the SEM; see Figure 19.
  • the amount of snowflakes increases with Sr 2+ , as shown in Figure 19b-f.
  • Energy dispersive X-ray spectroscopy (EDS) mapping was carried out on the CsPbo.9sSro.o2l2Br film, with results shown in Figure 27.
  • EDS Energy dispersive X-ray spectroscopy
  • the Pb 4f spectrum for the CsPb ⁇ 2Br film shows 4fs /2 and 4f7 /2 peaks at 137.9 and 142.8 eV, respectively, corresponding to the Pb 2+ cations.
  • the I 3d 3/2 and I 3ds /2 peaks are also evident in the I 3d spectrum for the CsPb ⁇ 2Br film; see Figure 20b.
  • the Pb 4fs /2 , Pb 4f7 /2 , I 3d 3/2 , and I 3ds /2 peaks shift to higher binding energy, indicating that the chemical structures of the surface have been modified.
  • Sr 2+ cations at the surface of the film are evident with the presence of Sr 3d 3/2 and 3ds /2 peaks at 134.4 and 136.3 eV, respectively.
  • CsPbo.98Sro .02 ⁇ 2Br and CsPbo.95Sro.o5l2Br films are 0.20 and 0.38.
  • the Sr/Pb atomic ratio drops dramatically to 0.07 and 0.13 for CsPbo.9sSro.o2l2Br and CsPbo.95Sro .05l2Br films.
  • these ratios are higher than the molar ratios used in the synthesis of the films, which are 0.02 and 0.05, respectively, for the
  • Figure 21a shows that the absorption onset of CsPbi- xS r x ⁇ 2Br is around 656-664 nm (1.87-1.89 eV) and there is no shift in the absorption onset with Sr content.
  • the absorption of the film improves when Sr is incorporated as long as it is limited to less than 5%.
  • the steady-state PL spectra of these films also show peaks at around 660-665 nm (see Figure 30), which are consistent with those in the absorbance spectra.
  • Time-resolved PL (tr-PL) decays for CsPbi- xS r xl 2Br/mp-Al203 glass are also measured and shown in Figure 21b.
  • the presence of the fast component (ii) in the PL decay is commonly assumed to indicate the presence of defect trapping, and the slow component ( 2) corresponds to the effective recombination lifetime.
  • the defect trapping lifetime, ii, of all of the films is relatively the same, with a value of 2 ns.
  • 2 increases from 11.1 ns to 17.1 ns, suggesting a better effective recombination lifetime. This suggests better surface passivation provided by the Sr- enriched surface, as is evident in the XPS results.
  • the excess Sr 2+ doping in the perovskite film enhances electron-hole recombination, which will have a detrimental effect on photovoltaic performance of the CsPbo.gsSro.os ⁇ Br device.
  • FT0/c-Ti0 2 /mp-Ti0 2 /CsPbi- x Sr x l 2 Br/P3HT/Au solar cells were fabricated. Results are shown in Figure 22 and Table 3. Table 3. Photovoltaic Parameters of FT0/c-Ti0 2 /mp-Ti0 2 / CsPbi- x Sr x l 2 Br/P3HT/Au Champion Devices under
  • Figure 23c shows the normalized V oc , J sc , FF, and PCE as a function of storage (25 °C, relative humidity ⁇
  • CsPbl2Br reference cell experienced V oc and FF drops after the heat treatment. This indicates that CsPbo.9sSro.o2l2Br has better thermal stability than CsPbl2Br.
  • the champion CsPbo.9sSro.o2l2Br cell delivered the highest PCE at 11.3%, with a V oc of 1.07 V, a J sc of 14.9 mA cm -2 , a FF of 0.71, and a stabilized efficiency at 10.8%.
  • Sr-doped CsPbl2Br showed better thermal stability.

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Abstract

La présente invention concerne un procédé de formation d'une pérovskite ayant la formule ABX3. Le procédé consiste à fournir un film de solution de précurseur destiné à former la pérovskite. La solution comprend un premier sel destiné à former le composant A et un mélange d'un second sel et d'un sel dopant destiné à former le composant B. Le composant X est formé à partir d'anions des sels. Le procédé consiste en outre à chauffer le film de solution de précurseur pour former la pérovskite et convertir le sel dopant en un métal du sel dopant. Un rapport molaire [second sel] : [sel dopant] dans la solution précurseur est tel que la pérovskite a une surface enrichie avec le métal du sel dopant par rapport à un volume de la pérovskite.
PCT/AU2018/051016 2018-04-11 2018-09-17 Procédé de formation d'une pérovskite WO2019195873A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021226191A1 (fr) * 2020-05-05 2021-11-11 Northwestern University Composés de pérovskite de césium et de rubidium plomb dopées à l'oxygène et au fluor pour la détection de rayonnement dur
CN114058067A (zh) * 2021-11-23 2022-02-18 南昌大学 一种制备钙钛矿量子点-聚合物多孔复合材料的方法
CN114808124A (zh) * 2022-03-16 2022-07-29 暨南大学 一种混合卤化物钙钛矿单晶及多晶薄膜的制备方法
LU501865B1 (en) * 2022-01-21 2023-07-24 Univ Hubei Arts & Science An efficient inorganic hybrid perovskite ink and its application

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US20170053746A1 (en) * 2015-08-18 2017-02-23 Massachusetts Institute Of Technology Planar mixed-metal perovskites for optoelectronic applications
WO2017037448A1 (fr) * 2015-09-02 2017-03-09 Oxford University Innovation Limited Pérovskite double

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US20170053746A1 (en) * 2015-08-18 2017-02-23 Massachusetts Institute Of Technology Planar mixed-metal perovskites for optoelectronic applications
WO2017037448A1 (fr) * 2015-09-02 2017-03-09 Oxford University Innovation Limited Pérovskite double

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LAU C. F. J. ET AL.: "Strontium-Doped Low-Temperature-Processed CsPbI2Br Perovskite Solar Cells", ACS ENERGY LETTERS, vol. 2, no. 10, 11 September 2017 (2017-09-11), pages 2319 - 2325, XP055642677, ISSN: 2380-8195, DOI: 10.1021/acsenergylett.7b00751 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021226191A1 (fr) * 2020-05-05 2021-11-11 Northwestern University Composés de pérovskite de césium et de rubidium plomb dopées à l'oxygène et au fluor pour la détection de rayonnement dur
EP4147279A4 (fr) * 2020-05-05 2024-05-22 Northwestern University Composés de pérovskite de césium et de rubidium plomb dopées à l'oxygène et au fluor pour la détection de rayonnement dur
CN114058067A (zh) * 2021-11-23 2022-02-18 南昌大学 一种制备钙钛矿量子点-聚合物多孔复合材料的方法
LU501865B1 (en) * 2022-01-21 2023-07-24 Univ Hubei Arts & Science An efficient inorganic hybrid perovskite ink and its application
CN114808124A (zh) * 2022-03-16 2022-07-29 暨南大学 一种混合卤化物钙钛矿单晶及多晶薄膜的制备方法
CN114808124B (zh) * 2022-03-16 2023-01-03 暨南大学 一种混合卤化物钙钛矿单晶及多晶薄膜的制备方法

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