CN112334602A - 透明导电膜 - Google Patents

透明导电膜 Download PDF

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Publication number
CN112334602A
CN112334602A CN201980043492.3A CN201980043492A CN112334602A CN 112334602 A CN112334602 A CN 112334602A CN 201980043492 A CN201980043492 A CN 201980043492A CN 112334602 A CN112334602 A CN 112334602A
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layer
transparent conductive
film
conductive film
organic compound
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CN201980043492.3A
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CN112334602B (zh
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B·丘
J-C·弗洛里斯
M·伦克尔
M·M·宋
J·W·容
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BASF Coatings GmbH
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BASF Coatings GmbH
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    • 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
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/44—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
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    • 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
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
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    • Y10T428/31678—Of metal

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Laminated Bodies (AREA)
  • Chemical Vapour Deposition (AREA)
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Abstract

本发明属于透明导电膜领域。特别地，本发明涉及一种透明导电膜，其包括：(a)第一叠层，其包括：‑至少两个包含TiO2、ZrO2或HfO2的层，和‑介于两个包含TiO2、ZrO2或HfO2的层之间的包含有机化合物的层，(b)金属层，和(c)第二叠层，其包括：‑至少两个包含ZnO的层，和‑介于两个包含ZnO的层之间的包含有机化合物的层，‑除锌以外的金属掺杂剂。

Description

透明导电膜
本发明属于透明导电膜领域，特别是有机-无机杂化透明导电膜。
透明导电膜广泛用作光电器件如太阳能电池或发光二极管中的电极。通常，氧化铟锡(ITO)用作导电膜中的材料。然而，ITO膜是脆性的，因此对于柔性器件具有有限的适用性。超晶格结构提供了一种替代方案。
US 5523585公开了一种超晶格结构，其通过在电子运动的方向上周期性重复第一和第二半导体材料区域而形成。然而，导电性和柔性是有限的。
US 2011/0212336A1公开了一种具有高电导率的导电叠层。然而，这种叠层是脆性的，因此对弯曲敏感。
JP 2016/012555A公开了据称是柔性的透明导电膜。然而，所用的金属氧化物是脆性的，因此不可能在没有裂纹的情况下围绕小半径弯曲。
US 2017/0121812A1公开了一种用于水分和氧阻挡应用的有机-无机超晶格。然而，没有指出如何由该方法获得透明导电膜。
本发明的目的是提供一种在弯曲后保持其导电性的透明导电膜。本发明进一步的目的在于提供一种制备这些膜的方法，该方法容易且可靠地得到高质量的膜。
这些目的通过一种透明导电膜实现，其包括：
(a)第一叠层，其包括：
-至少两个包含TiO2、ZrO2或HfO2的层，和
-介于两个包含TiO2、ZrO2或HfO2的层之间的包含有机化合物的层，
(b)金属层，和
(c)第二叠层，其包括：
-至少两个包含ZnO的层，和
-介于两个包含ZnO的层之间的包含有机化合物的层，
-除锌以外的金属掺杂剂。
本发明进一步涉及一种制备透明导电膜的方法，包括在衬底上沉积：
(a)第一叠层，其包括：
-至少两个包含TiO2、ZrO2或HfO2的层，和
-介于两个包含TiO2、ZrO2或HfO2的层之间的包含有机化合物的层，
(b)金属层，和
(c)第二叠层，其包括：
-至少两个包含ZnO的层，和
-介于两个包含ZnO的层之间的包含有机化合物的层，
-除锌以外的金属掺杂剂。
本发明进一步涉及本发明的膜作为光电子器件中的电极的用途。
本发明的优选实施方案可参见说明书和权利要求。不同实施方案的组合落入本发明的范围内。
本发明的膜是透明的。在本上下文中，透明意指导电金属氧化物膜透射平行于表面法线照射在膜上的550nm波长的光的强度的至少50％，更优选至少70％，特别是至少80％。
本发明的膜是导电的，这意味着该膜是电导性的。优选地，所述膜的方阻为1000Ω/sq或更小，更优选为500Ω/sq或更小，甚至更优选为200Ω/sq或更小，特别为100Ω/sq或更小。优选地，所述膜的电阻率为0.01Ω·cm或更小，更优选为3·10-3Ω·cm或更小，甚至更优选为10-3Ω·cm或更小，特别为3·10-4Ω·cm或更小。方阻和电阻率通常都在20℃的温度下测量，优选地，膜的方阻和电阻率使用四点探针技术测量。
本发明的膜包括第一叠层，该第一叠层包括包含TiO2、ZrO2或HfO2，优选TiO2的层。优选地，这些层包含至少50重量％的TiO2、ZrO2或HfO2，更优选至少70重量％的TiO2、ZrO2或HfO2，特别是至少90重量％的TiO2、ZrO2或HfO2。包含TiO2、ZrO2或HfO2的层可以是无定形的、部分结晶的或结晶的，优选其是结晶的。包含TiO2、ZrO2或HfO2的所述至少两个层可具有相同的厚度或不同的厚度，优选它们具有相同的厚度。包含TiO2、ZrO2或HfO2的层优选具有0.1-100nm，更优选1-10nm，特别是2-5nm的厚度。优选地，包含TiO2、ZrO2或HfO2的层具有均匀的厚度，这意味着在该层的最厚位置处的厚度小于最薄位置处的厚度的2倍，更优选小于最薄位置处的厚度的1.5倍。本发明的膜包括至少两个包含TiO2、ZrO2或HfO2的层，优选至少3个，更优选至少5个，特别是至少10个。
第一叠层进一步包括包含有机化合物的层。如果所述膜包括多于两个包含TiO2、ZrO2或HfO2的层，则该膜优选交替地包括包含TiO2、ZrO2或HfO2的层和包含有机化合物的层，从而使得包含有机分子的每个层都处于两个包含TiO2、ZrO2或HfO2的层之间，其中其他层可处于这些层之间。包含有机化合物的层优选比包含TiO2、ZrO2或HfO2的层薄。如果存在多于一个包含有机化合物的层，则它们可具有相同的厚度或不同的厚度，优选它们具有相同的厚度。包含有机化合物的层优选具有0.05-5nm，更优选0.1-1nm的厚度。包含有机化合物的层可为单层，即具有一个分子数量级的厚度，或者为亚单层。
包含有机化合物的层优选包含大于98重量％，优选大于99重量％，特别是完全或基本完全的非金属。甚至更优选地，非金属为C、H、O、N、S、Se和/或P。包含有机化合物的层可包含一种有机化合物或多于一种有机化合物，例如2种或3种。包含有机化合物的层优选包含含硫化合物。含硫化合物中的硫优选处于-2、-1或0的氧化态，即负二、负一或零，例如有机硫醇、有机硫醚或有机二硫醚。优选有机硫醇。含硫化合物可包含一个或多于一个硫原子。优选地，含硫化合物包含一个硫原子。更优选地，含硫化合物为芳族硫醇。硫醇可直接键合到分子的芳族部分上，或者通过连接基如亚甲基键合，优选其直接键合到芳族基团上。含硫化合物甚至更优选为苯硫酚衍生物。优选地，含硫分子进一步包含一个或多个羟基。下文给出了含硫化合物的一些优选实例。
Figure BDA0002859717000000041
特别优选4-巯基苯酚(C-1)、4-巯基苄醇(C-2)和2,3-二巯基丙醇(C-15)。还可制备具有不同有机分子的有机层，条件是至少一种有机分子是含硫的。
优选地，含硫化合物包含至少两个硫原子，更优选两个硫原子。含硫化合物中的硫原子彼此独立地为上述官能团的一部分。优选硫醇，更优选二硫醇。优选地，两个硫醇基直接或通过连接基如亚甲基连接到芳族体系如苯上。下文给出了包含两个硫原子的含硫化合物的一些优选实例。
Figure BDA0002859717000000051
如果包含有机化合物的层中的有机化合物包含羟基、硫醇或其他可脱质子化的基团，则该基团可保持质子化或脱质子化并配位到金属上，或者一些基团质子化而一些基团脱质子化并配位到金属上。
第一叠层具有高的相对介电常数。优选地，在室温和1MHz下的相对介电常数至少为10，更优选至少为20，特别是至少为50。第一叠层的厚度优选为2-60nm，更优选为5-40nm，特别为10-30nm。
本发明的膜进一步包括金属层。金属层可包含Li、Be、Na、Mg、Al、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Ga、Rb、Sr、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In Sn、Cs、Ba、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Hf、Ta、W、Re、Os Ir、Pt、Au、Hg、Tl、Bi。优选地，金属层包含Al、Cu、Ag、Au，特别是Ag。所述膜可包含一种或多于一种，例如两种或三种金属。金属层具有金属电导率，优选为至少105S/m，更优选为至少106S/m，特别为至少107S/m。在金属层和第一叠层之间可存在其他层。然而，优选地，金属层与第一叠层接触。金属层足够薄以允许可见光透射；优选地，金属层具有1-100nm，更优选2-50nm，甚至更优选3-30nm，特别是5-20nm，例如8-15nm，例如10nm的厚度。
本发明的膜包括第二叠层，该第二叠层包括至少两个包含ZnO(即氧化锌)的层。优选地，这些层包含至少50重量％的ZnO，更优选至少70重量％的ZnO，特别是至少90重量％的ZnO。包含ZnO的层可以是无定形的、部分结晶的或结晶的，优选是结晶的。所述至少两个包含ZnO的层可具有相同的厚度或不同的厚度，优选它们具有相同的厚度。包含ZnO的层优选具有0.1-100nm，更优选1-10nm，特别是2-5nm的厚度。优选地，包含ZnO的层具有均匀的厚度，这意味着该层的最厚位置处的厚度小于最薄位置处厚度的2倍，更优选小于最薄位置处厚度的1.5倍。本发明的膜包括至少2个包含ZnO的层，优选至少3个，更优选至少5个，特别是至少10个。
第二叠层进一步包括包含有机化合物的层。如果所述膜包括多于两个包含ZnO的层，则该膜优选交替地包括包含ZnO的层和包含有机化合物的层，以使得每个包含有机分子的层处于两个包含ZnO的层之间，其中这些层之间可存在其他层。包含有机化合物的层优选比包含ZnO的层薄。如果存在多于一个包含有机化合物的层，则它们可具有相同的厚度或不同的厚度，优选它们具有相同的厚度。包含有机化合物的层优选具有0.05-5nm，更优选0.1-1nm的厚度。包含有机化合物的层可为单层，即具有一个分子数量级的厚度，或者为亚单层。
第一叠层中的有机化合物的相同定义和优选实施方案适用于第二叠层。第一叠层中的有机化合物可与第二叠层中的有机化合物相同，或者可以是不同的，优选是相同的。
第二叠层进一步包含除锌以外的金属掺杂剂。金属掺杂剂可为Li、Be、Na、Mg、Al、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Ga、Rb、Sr、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In Sn、Cs、Ba、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Hf、Ta、W、Re、Os Ir、Pt、Au、Hg、Tl、Bi。优选地，金属掺杂剂为Mo、Ta、In、V、Sn、W、Mn、Al、Ga、Ti、Zr或Hf，特别为Al。所述膜可包含一种或多于一种，例如2种或3种除锌以外的金属掺杂剂。
所述膜通常包含比锌少的金属掺杂剂。优选地，金属掺杂剂和锌的原子比为10-10:0.1，更优选为10-9:0.01，特别为10-8:10-3。对金属掺杂剂所处的位置没有特别的限制，因为据认为至少一部分金属掺杂剂可以在膜中迁移。然而，优选地，金属掺杂剂的浓度在包含氧化锌的层和包含有机化合物的层之间的界面处最高。
在金属层和第二叠层之间可存在其他层。然而，优选地，金属层与第二叠层接触。因此，金属层通常处于第一和第二叠层之间，优选地，其位于第一和第二叠层之间并且与第一和第二叠层直接接触。第二叠层的厚度优选为10-100nm，更优选为20-80nm，特别为30-60nm，例如为35-50nm。
所述膜优选包括衬底，特别是透明衬底。优选地，衬底面向第一叠层，特别地，第一叠层与衬底接触。可使用各种透明衬底，例如玻璃或聚合物。优选聚合物。聚合物包括聚酯，例如聚对苯二甲酸乙二醇酯(PET)或聚萘二甲酸乙二醇酯(PEN)；聚酰亚胺；聚丙烯酸酯，例如聚甲基丙烯酸甲酯(PMMA)；聚丙烯酰胺；聚碳酸酯，例如聚(双酚A碳酸酯)；聚乙烯醇及其衍生物，例如聚乙酸乙烯酯或聚乙烯醇缩丁醛；聚氯乙烯；聚烯烃，例如聚乙烯(PE)或聚丙烯(PP)；聚环烯烃，例如聚降冰片烯；聚醚砜；聚酰胺，例如聚己内酰胺或聚(六亚甲基己二酰胺)；纤维素衍生物，例如羟乙基纤维素、羟丙基纤维素、甲基纤维素、甲基羟丙基纤维素或硝化纤维素；聚氨酯；环氧树脂；三聚氰胺甲醛树脂；酚醛树脂。聚合物包括共聚物，例如聚(乙烯-共聚-降冰片烯)或聚(乙烯-共聚-乙酸乙烯酯)。优选聚酯和聚环烯烃。
衬底可具有任何尺寸和形状。优选地，衬底为膜。衬底膜的厚度取决于应用。如果阻挡膜围绕大于10mm的半径弯曲，则衬底膜的厚度优选为100-1000μm，更优选为100-500μm，例如100-200μm。如果阻挡膜围绕小于10mm的半径弯曲，则衬底膜的厚度优选为1-100μm，更优选为10-70μm，例如40-60μm。
衬底的表面优选具有高平面性。在本发明的上下文中，高平面性意指表面上的最高点比表面上的最低点高不超过100nm，优选不超过50nm。平面性可用原子力显微镜，优选以轻敲模式测量。
衬底通常不能以高平面性获得，例如由于小的划痕或粘附到其表面的颗粒如灰尘。因此，优选地，阻挡膜进一步包括平坦化层，以避免诸如刺穿叠层的损坏。更优选地，平面化层处于衬底和所述叠层之间。在这种情况下，平坦化层可额外用于将衬底和叠层更好地保持在一起，特别是在弯曲或加热时。平面化层可包括有机聚合物，例如丙烯酸酯或环氧树脂，陶瓷，例如碳化物，例如SiC，或有机-无机杂化材料，例如聚烷基硅氧烷。优选有机聚合物。
通常，在施加叠层之前，通过在衬底上沉积构成平坦化层的材料来制备平坦化层。在有机聚合物的情况下，将包含单体的液体流延到衬底上，然后固化，例如通过加热或通过UV引发。优选UV引发，更优选地，包含单体的液体进一步包含固化助剂，例如官能化的二苯甲酮。优选地，包含单体的液体包含单官能和双官能单体的混合物，以使得在固化后获得交联的有机聚合物。通常，通过将材料溅射到衬底上来获得包含陶瓷的平坦化层。包含有机-无机杂化材料的平坦化层可通过在衬底上流延包含有机-无机前体的溶液、蒸发溶剂和缩合有机-无机前体(例如通过加热)来获得。这种方法通常称为溶胶-凝胶法。有机-无机前体的实例为烷基-三烷氧基硅烷。优选地，前体用可UV固化侧基如丙烯酸酯官能化。以此方式，有机-无机杂化材料可以交联。
优选地，构成平面化层的材料具有介于衬底材料的弹性模量和叠层的弹性模量之间的弹性模量，例如10-30GPa。测定弹性模量的方法描述于ISO527-1(塑料—拉伸性能的测定，2012)中。
本发明的膜对机械应力或应变特别不敏感。优选地，在将膜围绕0.5cm的半径弯曲500次之后，膜的方阻增加小于50％。
本发明的膜可以以各种方式制备。所述层可由溶液或气相沉积。优选气相沉积法。该类方法包括化学气相沉积(CVD)、热蒸发、溅射或原子层沉积(ALD)。也可将不同的方法组合，例如通过用一种方法沉积某些层，而用不同的方法沉积其他层。ALD优选用于第一和第二叠层的沉积。对于金属层，热蒸发、溅射和ALD是优选的，特别是热蒸发。简单起见，本发明上下文中的ALD包括原子层沉积以及分子层沉积或其混合。
实施该方法的典型压力为1500至10-5毫巴，优选为100至10-3毫巴，更优选为10至0.1毫巴。因此，该方法优选在压力可以调节的装置中进行，例如在真空室中。该方法的温度为-20℃至500℃，优选为0-300℃，特别为50-220℃。
为了沉积包含TiO2、ZrO2或HfO2的层，可使用各种含Ti、Zr或Hf的化合物。优选地，使用含金属-有机金属的化合物，例如烷基金属；金属烷氧基化物，例如四异丙氧基锆；环戊二烯加合物，例如二茂钛；金属卡宾；金属卤化物，例如四氯化钛；一氧化碳络合物。优选金属卤化物，特别是氯化物。
为了沉积包含ZnO的层，可使用各种含锌化合物。优选地，使用含金属-有机锌的化合物，例如烷基锌，例如二甲基锌；烷氧基锌，例如二甲氧基锌；环戊二烯加合物，例如二茂锌；卡宾锌，例如N,N'-二甲基咪唑-2-亚基锌；卤化锌，例如氯化锌。更优选地，含锌化合物为烷基锌，特别为C1-C4烷基锌。
沉积的含锌化合物通常必须转化为氧化锌。这可通过加热到含锌化合物的分解温度以上，优选在氧存在下加热来实现。优选地，通过使沉积的含锌化合物与含氧化合物如水、氧、臭氧或氧等离子体接触，而使其分解。
如果通过ALD制备包含ZnO的层，则优选实施至少1次，优选至少5次，更优选至少10次，特别是至少20次包括沉积含锌化合物和通过使其与含氧化合物接触而沉积含锌化合物的序列。通常，该序列实施不超过1000次。
为了沉积包含有机化合物的层，可优选使用上述化合物。优选地，将有机化合物沉积在沉积的金属-有机化合物上。然而，如果将有机化合物沉积在包含氧化锌的层上，则包含氧化锌的层的表面是反应性的，例如由于沉积的含锌化合物尚未与含氧化合物接触。
优选地，制备第二叠层的方法包括序列，该序列包括沉积包含氧化锌的层，沉积包含有机化合物的层以及沉积除锌以外的金属掺杂剂，其中该序列实施一次或优选多于一次，例如至少2次、至少3次、至少5次或者特别地至少10次，然后沉积另一包含氧化锌的层。所述序列可具有以下顺序：
(1)沉积包含氧化锌的层
(2)沉积包含有机化合物的层，和
(3)沉积除锌以外的金属掺杂剂。
或者，所述序列可具有以下顺序：
(1)沉积包含氧化锌的层
(2)沉积除锌以外的金属掺杂剂，和
(3)沉积包含有机化合物的层。
所述序列可包括两次沉积除锌以外的金属掺杂剂，例如以如下顺序：
(1)沉积包含氧化锌的层，
(2)沉积除锌以外的金属掺杂剂，
(3)沉积包含有机化合物的层，和
(4)沉积除锌以外的金属掺杂剂。
如果该方法是ALD方法，则通常在一个ALD循环中将表面暴露于含锌化合物或有机化合物1毫秒至30秒，优选10毫秒至5秒，特别是50毫秒至1秒。优选地，在将表面暴露于不同化学结构的含(半)金属化合物或含硫化合物之间用惰性气体吹扫衬底，通常0.1秒至10分钟，优选1秒至3分钟，特别是10秒至1分钟。
优选地，本发明的方法作为空间ALD方法进行，即含锌化合物、含金属化合物、有机化合物和含氧化合物通过相对于衬底移动的单独的孔。这意味着衬底移动，而孔保持不动；或者衬底保持不动，同时孔移动；或者衬底和孔都移动。优选地，运动速度为0.01-10m/s，更优选为0.02-1m/s，特别为0.05-0.3m/s。排列所述孔，以使得含锌化合物、含金属化合物、含氧化合物和有机化合物以对上述方法所述的顺序撞击衬底表面。为了避免在气相中反应，优选将惰性气体如氮气或氩气通过的孔朝向衬底表面置于含锌化合物、含金属化合物、含氧化合物和有机化合物通过的孔之间。
优选地，孔安装在转鼓上，衬底围绕该转鼓放置，优选地移动。该装置描述于WO2011/099858A1中。在衬底是柔性的情况下，有机-无机衬底因此可在所谓的辊到辊工艺中沉积在大衬底上。
本发明的膜可用作光电器件中的电极。光电器件的实例包括发光二极管、激光器、太阳能电池或光学传感器。
实施例
衬底制备
聚合物膜衬底是从聚对苯二甲酸乙二醇酯(PET)膜(厚度：125μm)切割的。将PET聚合物膜衬底用丙酮、乙醇、去离子水清洁，并用氮气吹干以除去污染物。
表征
使用光谱椭偏测厚仪(FS-1多波长椭偏测厚仪，Film Sense)测量包含氧化锌的层的厚度。通过原子力显微镜(AFM，XE-100)研究膜的形貌。使用四点探针技术(HP4155C，Agilent Technologies)测量膜的电导率。使用UV-VIS光谱仪(UV-VIS 8453，AgilentTechnologies)获得UV-可见光谱。
实施例1(对比)
使用氯化钛(IV)(TiCl4)和去离子水(H2O)作为ALD前体将TiO2沉积在PET衬底上。氩气(Ar)同时作为载气和吹扫气体。在20℃下蒸发DEZ和H2O。该循环由1秒暴露于DEZ、5秒Ar吹扫、1秒暴露于H2O和5秒Ar吹扫组成。Ar的总流速为100sccm。在该程序期间，温度保持在100℃下，压力保持在400毫巴下。该循环实施875次，产生35nm厚的TiO2膜。
通过热蒸发在TiO2膜上沉积Ag层。
使用二乙基锌(DEZ)和去离子水(H2O)作为ALD前体将包含氧化锌的层沉积到Ag层上。氩气(Ar)同时作为载气和吹扫气体。在20℃下蒸发DEZ和H2O。该循环由1秒暴露于DEZ、5秒Ar吹扫、1秒暴露于H2O和5秒Ar吹扫组成。Ar的总流速为100sccm。在该程序期间，温度保持在100℃下，压力保持在400毫巴下。ALD法的ZnO薄膜的生长速度为
Figure BDA0002859717000000111
/循环。实施该循环233次。
随后，使用三甲基铝(TMA，Sigma Aldrich：99％)和4-巯基苯酚(4MP，SigmaAldrich：97％)作为前体制备包含有机化合物的层。将反应温度降至145℃。Ar同时用作载气和吹扫气体。TMA和4MP分别在20℃和80℃下蒸发。ALD循环由1秒暴露于TMA、5秒Ar吹扫、5秒暴露于4MP、60秒Ar吹扫、1秒暴露于TMA和5秒Ar吹扫组成。实施该循环1次。
实施例2(对比)
在PET衬底上，如实施例1中那样沉积TiO2膜和Ag膜。使用二乙基锌(DEZ)和去离子水(H2O)作为ALD前体将包含氧化锌的层沉积到Ag层上。氩气(Ar)同时作为载气和吹扫气体。在20℃下蒸发DEZ和H2O。该循环由1秒暴露于DEZ、5秒Ar吹扫、1秒暴露于H2O和5秒Ar吹扫组成。Ar的总流速为100sccm。在该程序期间，温度保持在100℃下，压力保持在400毫巴下。ALD法的ZnO薄膜的生长速度为
Figure BDA0002859717000000121
/循环。实施该循环233次。
随后，使用三甲基铝(TMA，Sigma Aldrich：99％)和2,3-二巯基-1-丙醇(DMP，Sigma Aldrich：98％)作为前体制备包含有机化合物的层。将反应温度降低至145℃。Ar同时用作载气和吹扫气体。TMA和4MP分别在20℃和80℃下蒸发。ALD循环由1秒暴露于TMA、5秒Ar吹扫、5秒暴露于4MP、60秒Ar吹扫、1秒暴露于TMA和5秒Ar吹扫组成。实施该循环1次。
将如前文所述的包含氧化锌的层和包含有机化合物的层的沉积工艺交替进行14次，产生35nm厚的第二叠层。
实施例3(本发明)
在PET衬底上，通过首先使用氯化钛(IV)(TiCl4)和去离子水(H2O)作为ALD前体沉积TiO2层来制备第一叠层。氩气(Ar)同时作为载气和吹扫气体。在20℃下蒸发DEZ和H2O。该循环由1秒暴露于DEZ、5秒Ar吹扫、1秒暴露于H2O和5秒Ar吹扫组成。Ar的总流速为100sccm。在该程序期间，温度保持在100℃下，压力保持在400毫巴下。ALD法的TiO2薄膜的生长速率为
Figure BDA0002859717000000122
/循环。实施该循环266次。
随后，使用氯化钛(IV)(TiCl4)和2,3-二巯基-1-丙醇(DMP，Sigma Aldrich：98％)作为前体制备包含有机化合物的层。将反应温度降至145℃。Ar同时用作载气和吹扫气体。TiCl4和DMP分别在20℃和80℃下蒸发。ALD循环由1秒暴露于TiCl4、5秒Ar吹扫、5秒暴露于DMP、60秒Ar吹扫、1秒暴露于TiCl4和5秒Ar吹扫组成。实施该循环1次。
交替实施如上所述的包含TiO2的层和包含有机化合物的层的沉积工艺7次，产生厚度为19nm的第一叠层。
在第一叠层上，如实施例1那样沉积Ag层且如实施例2那样沉积第二叠层，不同之处在于第二叠层具有40nm的厚度，因为如上所述的包含氧化锌的层和包含有机化合物的层交替进行16次。
实施例4(本发明)
重复实施例3，第一个不同之处在于第一叠层具有24nm的厚度，因为如上所述的包含TiO2的层和包含有机化合物的层的沉积交替进行11次。第二个不同之处在于第二叠层具有45nm的厚度，因为如上所述的包含氧化锌的层和包含有机化合物的层交替进行18次。
方阻
在沉积后，在围绕0.5cm的半径弯曲500次和1000次后测量实施例1-4中获得的膜的方阻。
实施例 初始方阻，Ω/sq 方阻(500次弯曲)，Ω/sq 方阻(1000次弯曲)，Ω/sq
1 25 647 4892
2 20 326 2890
3 23 35 245
4 21 29 95

Claims (15)

1.一种透明导电膜，其包括：
(a)第一叠层，其包括：
-至少两个包含TiO2、ZrO2或HfO2的层，和
-介于两个包含TiO2、ZrO2或HfO2的层之间的包含有机化合物的层，
(b)金属层，和
(c)第二叠层，其包括：
-至少两个包含ZnO的层，和
-介于两个包含ZnO的层之间的包含有机化合物的层，
-除锌以外的金属掺杂剂。
2.根据权利要求1所述的透明导电膜，其中包含TiO2、ZrO2或HfO2的层具有1-10nm的厚度。
3.根据权利要求1所述的透明导电膜，其中包含ZnO的层具有1-10nm的厚度。
4.根据权利要求1-3中任一项所述的透明导电膜，其中金属层包含Al、Cu、Ag或Au。
5.根据权利要求1-4中任一项所述的透明导电膜，其中金属层具有3-30nm的厚度。
6.根据权利要求5所述的透明导电膜，其中所述有机化合物为有机硫醇。
7.根据权利要求1-6中任一项所述的透明导电膜，其中第一叠层具有5-40nm的厚度。
8.根据权利要求1-7中任一项所述的透明导电膜，其中所述膜进一步包括透明柔性衬底。
9.根据权利要求1-8中任一项所述的透明导电膜，其中所述膜具有200Ω/sq或更小的方阻。
10.根据权利要求1-8中任一项所述的透明导电膜，其中所述膜具有0.02Ω·cm或更小的电阻率。
11.根据权利要求1-10中任一项所述的透明导电膜，其中在将所述膜围绕1cm的半径弯曲500次之后，所述膜的方阻增加小于10％。
12.一种制备透明导电膜的方法，包括在衬底上沉积：
(a)第一叠层，其包括：
-至少两个包含TiO2、ZrO2或HfO2的层，和
-介于两个包含TiO2、ZrO2或HfO2的层之间的包含有机化合物的层，
(b)金属层，和
(c)第二叠层，其包括：
-至少两个包含ZnO的层，和
-介于两个包含ZnO的层之间的包含有机化合物的层，
-除锌以外的金属掺杂剂。
13.根据权利要求12所述的方法，其中所述沉积通过原子层沉积进行。
14.根据权利要求13或14所述的方法，其中所述沉积在100-220℃的温度下进行。
15.根据权利要求1-11中任一项的膜作为光电器件中的电极的用途。
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