WO2016095828A1 - 聚合物-金属化合物复合墨水及其制备方法与应用 - Google Patents

聚合物-金属化合物复合墨水及其制备方法与应用 Download PDF

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WO2016095828A1
WO2016095828A1 PCT/CN2015/097676 CN2015097676W WO2016095828A1 WO 2016095828 A1 WO2016095828 A1 WO 2016095828A1 CN 2015097676 W CN2015097676 W CN 2015097676W WO 2016095828 A1 WO2016095828 A1 WO 2016095828A1
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Prior art keywords
polymer
composite ink
metal compound
film
ink according
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PCT/CN2015/097676
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English (en)
French (fr)
Inventor
王宜玲
骆群
武娜
马昌期
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中国科学院苏州纳米技术与纳米仿生研究所
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Priority claimed from CN201410787773.9A external-priority patent/CN105778619B/zh
Priority claimed from CN201510706292.5A external-priority patent/CN106611818B/zh
Application filed by 中国科学院苏州纳米技术与纳米仿生研究所 filed Critical 中国科学院苏州纳米技术与纳米仿生研究所
Priority to DK15869335.8T priority Critical patent/DK3235869T3/da
Priority to US15/535,617 priority patent/US11345824B2/en
Priority to EP15869335.8A priority patent/EP3235869B1/en
Priority to EP19201375.3A priority patent/EP3623426B1/en
Publication of WO2016095828A1 publication Critical patent/WO2016095828A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G28/00—Compounds of arsenic
    • C01G28/005—Oxides; Hydroxides; Oxyacids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • 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 particularly relates to a polymer-metal compound composite ink, and a preparation method and application thereof, for example, in an optoelectronic device, belonging to the field of optoelectronic semiconductor materials and devices.
  • novel solution-processable optoelectronic devices based on organic semiconductor materials, such as organic solar cells, perovskite solar cells, organic electroluminescent diodes (OLEDs), etc.
  • organic semiconductor materials such as organic solar cells, perovskite solar cells, organic electroluminescent diodes (OLEDs), etc.
  • OLEDs organic electroluminescent diodes
  • Such novel photoelectric conversion devices typically have a sandwich multilayer structure comprising an active layer and an electrode comprising a cathode and an anode.
  • the electrode is mainly a process of completing electron or hole injection (such as electroluminescence device) or collection (solar cell device).
  • the work function between the electrode and the photoelectric active layer does not match, and an interface barrier exists, which affects the injection or collection efficiency of electrons or holes, thereby affecting device performance.
  • an interface modification layer between the electrode and the active layer the surface function of the electrode can be adjusted, so that an ohmic contact is formed between the electrode and the photoelectric active layer, thereby reducing electron injection or collection efficiency, and achieving the purpose of improving device performance.
  • Electrode modification materials include two major categories: metal oxides and polymers.
  • Metal oxides such as zinc oxide, titanium oxide, tin oxide, etc. (especially suitable for cathode modification) and molybdenum oxide, cerium oxide, nickel oxide, etc. (especially suitable for anode modification) have the advantages of good electrical conductivity and high material stability. It is an excellent electrode interface modification material.
  • conventional metal oxide thin films are mostly deposited by vacuum sputtering, which is not compatible with ink-based printing methods. The preparation of various nanoparticles by the solution method can meet the requirements of the solution method for processing organic photoelectric devices.
  • the particle size of the metal oxide is reduced to a nanometer scale, such as: 3-50 nm, especially when it is lowered to about 5-15 nm, the metal nanoparticles can be dispersed in a solvent to satisfy the solution process.
  • a solvent for example, it has been reported to prepare zinc oxide nanoparticles (ZnO), titanium oxide nanoparticles (TiO 2 ), and cerium-doped titanium oxide nanoparticles (TiO 2 : Cs), molybdenum oxide nanoparticles (MoO 3 ), and oxidation by a solution method.
  • ZnO zinc oxide nanoparticles
  • TiO 2 titanium oxide nanoparticles
  • Cerium-doped titanium oxide nanoparticles TiO 2 : Cs
  • MoO 3 molybdenum oxide nanoparticles
  • oxidation by a solution method.
  • ⁇ (V 2 O 5 ) nanoparticles and nickel oxide (NiO) nanoparticles as electrode modification layers can effectively improve device efficiency and device
  • the anode modification layer is mainly 3,4-ethylenedioxythiophene polymer-polystyrene sulfonate, ie (PEDOT:PSS) conductive polymer, which has high conductivity and The film quality is high, but the deposition of PEDOT:PSS on the organic film layer usually requires the addition of a surfactant in PEDOT:PSS to modify it or reduce the surface energy by surface treatment of the organic active layer. However, late removal of surfactants is difficult.
  • the surface of the organic active layer is treated by plasma or ultraviolet ozone, and the requirements on the device are also high, and it is possible to destroy the organic film to some extent and shorten the life of the device.
  • Polymer materials for cathodic modification generally referred to as ionic conjugated polymers such as polyfluorene, polythiophene, polycarbazole and their derivatives, or non-conjugated polymers such as polyacetimidate And other derivatives.
  • ionic conjugated polymers such as polyfluorene, polythiophene, polycarbazole and their derivatives
  • non-conjugated polymers such as polyacetimidate And other derivatives.
  • the synthetic preparation method of the ionic polymer electrolyte based on the conjugated polymer material is complicated and the material cost is high.
  • Another class of non-conjugated polymers for cathode interface modification is described (see, for example, Science 2012, 336 (6079), 327-332).
  • conjugated polymer electrolytes such non-conjugated polymers are commercially mature polymers that can be prepared on a large scale, with low cost and mature technology.
  • the device performance shows a very strong film thickness dependence, that is, the device performance is very sensitive to the thickness of the electrode interface modification layer, and the optimum thickness is usually Between 10-15 nm, the device preparation process has brought great difficulty.
  • the metal oxide nano-particle/conductive polymer double-layer structure is used as the electrode modification layer, that is, a metal oxide nano-particle film is deposited on the surface of the electrode, and then a layer of conjugated polymer polyelectrolyte film is deposited thereon.
  • the method can solve the problem of unevenness of metal nanoparticle coating to some extent. However, this method still has the problem of agglomeration of nano metal oxide particles during the deposition of the first metal oxide film; in addition, this method also increases the number of electrode modification interfaces and increases the influence factor of device performance. It also makes the fabrication process of the device more complicated.
  • the nano-cluster materials have the function of modifying the work function.
  • the nano-cluster materials have the advantages of low material, simple ink configuration, good solubility, and solution processing.
  • Polyoxometalates can serve as an interfacial modification layer for the anode.
  • some of the reported phosphomolybdic acid (PMA) can be used as an anode buffer layer in an inverted solar cell.
  • PMA phosphomolybdic acid
  • polyoxometallates can also serve as cathode interface modification layers.
  • H 3 PW 12 O 40 can be used as a cathode buffer layer for light emitting diodes and organic solar cells.
  • such materials also have a problem of agglomeration and a large film roughness.
  • the main object of the present invention is to provide a polymer-metal compound composite ink and a preparation method thereof, which can be used for electrode interface modification, and can realize adjustment of the surface work function of the electrode, thereby overcoming the present There are technical deficiencies.
  • the technical solution adopted by the present invention includes:
  • At least one polymer is At least one polymer
  • At least one metal compound material selected from the group consisting of polyoxometallate compounds and nano metal oxides, and
  • At least one solvent for complexing with the remaining components of the composite to form a homogeneous fluid dispersion At least one solvent for complexing with the remaining components of the composite to form a homogeneous fluid dispersion.
  • the metal compound material is selected from the group consisting of polyoxometallate compounds.
  • the polymer comprises a conjugated polymer and/or a non-conjugated polymer.
  • the polymer-metal compound composite ink comprises:
  • At least one polymer having a fatty amine unit At least one polymer having a fatty amine unit
  • At least one nano metal oxide is At least one nano metal oxide
  • At least one organic alcohol used as the solvent At least one organic alcohol used as the solvent.
  • the nano metal oxide comprises a metal element selected from the group consisting of molybdenum, vanadium, tungsten, nickel, titanium, tin, and zinc.
  • the nano metal oxide may further comprise a metal and/or a non-metal element different from any of the metal elements and oxygen elements in the element group.
  • Embodiments of the present invention also provide a method of preparing the polymer-metal compound composite ink, comprising: uniformly mixing the polymer and the metal compound material in a solvent to form the composite ink.
  • Embodiments of the present invention also provide a film formed mainly of the polymer-metal compound composite ink.
  • the embodiment of the invention further provides a method for preparing a film, comprising: forming the film by applying or coating the polymer-metal compound composite ink onto a substrate by coating or printing.
  • Embodiments of the present invention also provide an apparatus comprising the film.
  • the polymer-metal compound composite ink and the film raw material of the invention have wide sources, are easy to prepare, and have low cost;
  • a film formed by using the polymer-metal compound composite ink of the present invention as an interface modifying material can be mentioned
  • the film denseness of the high interface modification layer reduces the surface roughness of the interface modification layer, thereby improving the performance of the device, for example, the surface work function adjustment of the electrode can be realized when applied to the electrode interface modification;
  • the polymer-metal compound composite ink of the present invention can be deposited into a film by various common methods such as spin coating, blade coating, inkjet printing, etc., and has the advantages of simple processing technology and the like;
  • the formed device exhibits a lower film thickness dependence, thereby being able to reduce the process requirements for device fabrication and to improve the device. Yield rate.
  • FIG. 1 is a schematic structural view of a solar cell device in Embodiment 1;
  • Example 2 is a JV graph of a P3HT:PC 61 BM system solar cell using ZnO, ZnO:PEI, PEI as a cathode modification layer in Example 1;
  • 3a-3b are AFM diagrams of the ZnO thin film and the ZnO:PEI thin film in Example 1, respectively.
  • Embodiment 4 is a schematic structural view of a solar cell in Embodiment 3.
  • Fig. 5a is an absorption spectrum diagram of a PMA, PEDOT: PSS, PMA: PEDOT: PSS film in Example 3.
  • Fig. 5b is an absorption spectrum chart of PEDOT:PSS, PMA:PEDOT:PSS deposited on P3HT:PC 61 BM in Example 3, respectively.
  • FIGS. 6a-6c are AFM diagrams of PTB7: PC 61 BM film, PTB7: PC 61 BM/PMA film, PTB7: PC 61 BM/PMA: PEDOT: PSS film in Example 3, respectively.
  • FIG. 7a-7b are JV graphs of a PTB7:PC 61 BM solar cell using PMA, PEDOT:PSS, PMA:PEDOT:PSS, vapor deposited MoO 3 (e-MoO 3 ) as an anode modification layer in Example 3 . .
  • 8a-8d are stability test diagrams of an inverted structure device using PMA, PEDOT:PSS, PMA:PEDOT:PSS, and vapor-deposited MoO 3 (e-MoO 3 ) as an anode modification layer.
  • Figure 9 is a J-V curve of the device obtained in Example 5.
  • One aspect of the invention provides, in some embodiments, a polymer-metal compound composite ink comprising:
  • At least one polymer is At least one polymer
  • At least one metal compound material selected from the group consisting of polyoxometallate compounds and nano metal oxides, and
  • At least one solvent for complexing with the remaining components of the composite ink to form a uniform fluid dispersion At least one solvent for complexing with the remaining components of the composite ink to form a uniform fluid dispersion.
  • the polymer-metal compound composite ink is a polymer-nano metal oxide composite ink comprising:
  • At least one polymer having a fatty amine unit At least one polymer having a fatty amine unit
  • At least one nano metal oxide is At least one nano metal oxide
  • At least one organic alcohol used as a solvent At least one organic alcohol used as a solvent.
  • the polymer in the ink provided by the first embodiment of the present invention, can be effectively filled in the space between the metal oxide nanoparticles, thereby improving the compactness and uniformity of the composite film and reducing the surface of the electrode interface modification layer. Roughness.
  • the fatty amine unit contained in the polymer in the ink formulation can adjust the work function of the metal oxygen compound, reduce the surface defect density of the metal oxide in the film, increase the carrier concentration, and the carrier mobility. In order to adjust the modification performance of the polymer-nanometal oxide film on the electrode interface, thereby changing the application performance of the photovoltaic device.
  • the fatty amine unit comprises a primary, secondary or tertiary aliphatic amine, ie one of the following molecular structural units in the molecule:
  • n, p are independently selected from integers from 1-12.
  • the phrase "containing" means that the molecule contains at least one of the above structural units. Further, the above structural unit may be in the main chain of the polymer molecule, or may be in the side chain of the polymer molecule, or may contain the above-described fatty amine structural unit in both the main chain and the side chain of the molecule.
  • the polymer containing the aliphatic amine unit provided by the present invention is selected from the group consisting of linear or branched polyethyleneimine, terminal ethoxylated or ethylated polyethyleneimine, and polyethyleneimine. a copolymer of a fragment, or a mixture of the above polymers.
  • the above-mentioned linear or branched polyethyleneimine, terminal ethoxylated or ethylated polyethyleneimine, and the copolymer containing the polyethyleneimine fragment constructed thereon are industrially very Mature chemical products, with mature materials preparation process, stable product performance, etc., are a preferred way to implement the solution of the present invention. Except In addition, any ratio mixture of the above polymers can also be applied to the solution of the present invention.
  • the nano metal oxide may also be selected from, but not limited to, oxides containing elements such as zinc, titanium, molybdenum, vanadium, tungsten, nickel, and the like, and other oxides doped with other elements.
  • oxides containing elements such as zinc, titanium, molybdenum, vanadium, tungsten, nickel, and the like, and other oxides doped with other elements.
  • the nano metal oxide has a particle size of usually 3 to 50 nm, more preferably 5 to 15 nm.
  • the solvent is preferably an organic solvent containing at least one organic alcohol.
  • the addition of an organic alcohol to the composite ink can ensure that the nano metal oxide particles do not undergo significant agglomeration, thereby effectively stabilizing the formulated ink.
  • the organic alcohol is selected from, but not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, ethylene glycol monomethyl ether.
  • a mixed alcohol solvent formed by mixing two or more kinds of the above organic alcohols may also be used to stabilize the nano metal oxide particles.
  • the solvent of the present invention may further include an auxiliary organic solvent, which may be selected from, but not limited to, one of acetone, chloroform, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene or Two or more types are used for dispersing and stabilizing the configured composite ink, adjusting the surface tension of the composite ink, and improving the film forming performance of the configured composite ink.
  • an auxiliary organic solvent which may be selected from, but not limited to, one of acetone, chloroform, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene or Two or more types are used for dispersing and stabilizing the configured composite ink, adjusting the surface tension of the composite ink, and improving the film forming performance of the configured composite ink.
  • the weight-to-volume concentration of the polymer-metal oxide nanoparticles in the composite ink of the present invention is from 0.5 to 60 mg/mL.
  • the lower solids content results in insufficient deposition of complexes during processing of the composite film, and higher solids concentrations tend to cause solids to precipitate.
  • the weight mixing ratio of the polymer to the nano metal oxide is between 1:25 and 1:2.5, and the excessively high polymer will weaken the metal oxide to improve the stability of the modified layer.
  • the too low polymer ratio makes it difficult to uniformly disperse the nano metal oxide particles, resulting in the inability to form a dense composite film.
  • a more preferred ratio is between 1:6-1:4.
  • a method of preparing the polymer-nanometal oxide composite ink includes mixing a dispersion of a nano metal oxide with a solution of the polymer to form the composite ink.
  • preparation method may include the following steps:
  • the organic solvent 1 or the organic solvent 2 is at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, ethylene glycol monomethyl ether or A variety.
  • the choice of solvent requires a combination of the dispersion properties of the nanometal oxide in different solvents and the solvent requirements of the subsequent film deposition process.
  • an organic solar cell with an ITO/PEDOT:PSS/P3HT:PC 61 BM/ZnO:PEI/Al structure as an example, in order to avoid the solvent-on-optical active layer P3HT in the process of spin-coating the cathode modified layer ZnO: PEI: For PC 61 BM, solvents such as chlorobenzene and dichlorobenzene should be avoided.
  • the ZnO nanoparticles are selectively dissolved in a chloroform solvent, and the PEI is dissolved in methanol, and then the two are mixed.
  • the inverted structure organic solar cell with the structure of ITO/ZnO:PEI/P3HT:PC 61 BM/MoO 3 /Al is prepared, since ZnO:PEI is directly prepared on the surface of ITO, there is no solvent damage to the underlying material.
  • the problem therefore, can be configured according to the needs of the printing process, such as n-butanol or chlorobenzene.
  • the surface tension of the solvent can be adjusted to improve the contact performance of the ink with the substrate.
  • the invention also provides the use of the polymer-nanometal oxide composite ink in the preparation of photovoltaic devices.
  • the present invention provides a polymer-nanometal oxide composite film mainly formed of the polymer-nano metal oxide composite ink, wherein a film formation method including coating is employed. Or printing methods, etc.
  • the polymer-nanometal oxide conforming film is typically deposited on the substrate material during the actual deposition preparation process.
  • the substrate material may include, but is not limited to, glass, plastic, paper, and metal foil such as stainless steel, aluminum foil, and the like.
  • the coating method may include, but is not limited to, a spin coating film, a knife coating, a slit coating, and the like; the printing method includes inkjet printing, screen printing, gravure printing, flexographic printing, and the like.
  • the polymer-nanometal oxide composite film of the present invention may also be deposited on some transparent or opaque conductive film.
  • a transparent or opaque conductive film between the composite film of the present invention and the above-mentioned base material.
  • the transparent conductive film comprises: an indium tin oxide (ITO) film, a fluorine-doped tin oxide (FTO), a metal grid line film, a nano wire film, etc.
  • the opaque conductive film comprises: a nano metal film prepared by a printing method or A metal or alloy nanofilm deposited by vacuum, such as an Al film, an Al:Mg alloy film, or the like.
  • the polymer-nanometal oxide composite film provided by the present invention can also be deposited. On the surface of the functional film. These functional film surfaces include a light-emitting layer or charge transport layer in an organic electroluminescent device, a photoactive layer or a charge transport layer in an organic solar cell, or a perovskite crystal layer or a charge transport layer in a perovskite solar cell.
  • the polymer-nanometal oxide composite film provided by the invention can be deposited on the surface of the above functional film to prepare a conventional upright type organic photoelectric device, and can also be used for preparing a laminated organic photoelectric device, such as a laminated OLED, a laminate. Organic solar cells, or laminated perovskite solar cells.
  • the present invention discloses the use of a polymer-nanometal oxide composite film in an optoelectronic device.
  • the polymer-nanometal oxide composite film of the invention can effectively adjust the surface work function of the electrode and improve the interface contact performance between the electrode and the photoelectric active layer. Therefore, the composite film of the present invention can be used in an electronic device having photoelectric conversion characteristics, for example, as an electrode interface modification layer of a cathode.
  • Typical photovoltaic devices refer to those photovoltaic devices having electro-optical and/or photo-electric conversion characteristics, such as, but not limited to, solar cell devices or electroluminescent diode devices.
  • the nanoparticles obtained by the reaction are subjected to a static-washing precipitation-centrifugation-ultrasonic dispersion multi-step treatment to finally obtain an alcohol-dispersed ZnO nanoparticle dispersion.
  • the reaction solution was allowed to stand for 3 h, the supernatant was removed, a certain amount of methanol was added to the lower layer and stirred for 10 min. After standing overnight, the supernatant was removed, a certain amount of methanol was added to the precipitate, and centrifuged at 4000 rpm for 10 min to remove the supernatant.
  • the lower white precipitate is retained as nano ZnO particles, and the nano ZnO particle dispersion is obtained by ultrasonic dispersion with a chloroform-methanol mixed solvent.
  • the polymer-nano metal oxide composite ink is obtained by mixing a dispersion of the nano metal oxide particles and a dispersion of the polymer by different volume ratios.
  • ZnO:PEI composite ink ZnO dispersion and PEI dispersion are mixed according to different volume ratios and obtained by ultrasonic dispersion.
  • the polymer-nano metal oxide composite ink can be deposited on the surface of the ITO electrode or the organic photoactive layer by spin coating, knife coating or the like to obtain a cathode modified layer.
  • a composite cathode modification layer is spin-coated on the surface of the cathode in an inverted structure organic optoelectronic device.
  • the nano metal oxide-conductive polymer composition prepared by the process of the invention is used as a cathode modification layer of an organic photoelectric device, and has better film forming property and higher stability, and is simple in operation, compared with a conventional cathode modification layer material.
  • the experiment has good repeatability, and the organic photoelectric device can be prepared by printing in a better combination with the process.
  • the polymer-metal compound composite ink is a polymer-polyoxometal compound composite ink comprising:
  • At least one polymer is At least one polymer
  • At least one polyoxometalate compound and,
  • At least one solvent for complexing with the remaining components of the composite ink to form a uniform dispersion At least one solvent for complexing with the remaining components of the composite ink to form a uniform dispersion.
  • the composite material is a fluid homogeneous dispersion system, particularly a homogeneous liquid phase dispersion system, and thus can be considered as a polymer-polyoxometal compound ink.
  • the ink provided by the second embodiment of the present invention by uniformly mixing the polymer with the polyoxometal compound, the agglomeration of the polyoxometal compound can be reduced, the film formation uniformity can be improved, and the polymer can The pores between the polyoxometal compound are effectively filled, so that the compactness and uniformity of the composite film can be improved, and the roughness of the surface of the interface modification layer can be lowered.
  • the polymer can also function to adjust the work function of the polyoxometal compound in the composite interface layer, thereby changing the application performance of the photovoltaic device.
  • the polymer may include a conjugated polymer such as polyaniline, polythiophene, polypyrrole, polyselenophene, polyfluorene or a derivative thereof, or a polysulfonic acid or polyp-toluenesulfonic acid. Any one or a combination of two or more of the conjugated polymers is not limited thereto.
  • the polymer may be poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS), which is useful for organic as well as organic/inorganic composites. In optoelectronic devices.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)
  • the polyoxometal compound may be selected from the group consisting of polyoxometallate compounds containing any one or more of metal molybdenum, tungsten, and vanadium, but is not limited thereto.
  • polyoxometal compound may further contain an element such as phosphorus, silicon, germanium or arsenic, but is not limited thereto.
  • the polyoxometal compound may include a Keggin-type polyoxometal compound such as: [BM 12 O 40 ] n- , [PM 12 O 40 ] n- , [SiM 12 O 40 ] n- , [GeM 12 O 40 ] n- , [AsM 12 O 40 ] n- , [AlM 12 O 40 ] n- (M is a metal molybdenum, tungsten or vanadium, n is a positive integer), or Wells- a Dawson type polyoxometal compound such as: [P 2 M 18 O 62 ] n- , [As 2 M 18 ] n- (M is a metal molybdenum, tungsten, n is a positive integer), a Lindqvist type polyoxometalate compound, Such as: [Mo 6 O 19 ] 2- , [W 6 O 19 ] 2- and polymolybdic acid ([Mo 8 O 26)
  • the polyoxometallate compound may be a metal polyacid or a metal polyacid salt such as an ammonium salt, a sodium salt, a potassium salt or the like.
  • the weight ratio of the polymer to the polyoxometal compound is preferably from 1:0.1 to 1:15, particularly preferably from 1:1 to 1:3. More preferably, it is about 1:1. Excessive polymer ratio will weaken the role of nanomaterials in improving the stability of the modified layer. It is difficult to uniformly disperse the nanomaterial, resulting in the inability to form a dense composite film.
  • the solvent is mainly for facilitating dispersion of a polymer and a polyoxometal compound, particularly an ink.
  • the solvent may be selected from water, an organic alcohol or a mixture of water and an organic alcohol, and the like.
  • the organic alcohol may be selected from, but not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, ethylene glycol monomethyl ether and the like.
  • a mixed alcohol solvent formed by mixing two or more kinds of the above organic alcohols may be used to stabilize the inorganic nanoclustered particles.
  • the solvent may further include an auxiliary organic solvent, which may be selected from, but not limited to, any one or two of acetone, chloroform, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, or both.
  • an auxiliary organic solvent which may be selected from, but not limited to, any one or two of acetone, chloroform, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, or both.
  • the above is mainly used for dispersing and stabilizing the ink, adjusting the surface tension of the ink, and improving the film forming performance of the ink.
  • the polymer-polyoxometal compound compound in the polymer-polyoxometal compound composite ink, has a weight/volume concentration of 0.5-20 mg/mL, preferably 3-8 mg/ mL.
  • a lower solids content will result in insufficient deposition of the composite during processing of the composite to produce a film, and higher solids concentrations tend to cause solids to precipitate.
  • the polymer-polyoxometal compound composite ink may also be combined with other inks to form a composite ink in some embodiments.
  • One aspect of the present invention also provides a method of making a polymer-polyoxometal compound composite ink comprising: uniformly mixing a polymer with a polyoxometallate compound in a solvent to form the composite ink.
  • the preparation method comprises: dissolving and/or dispersing a polymer in a solvent to form a first system, and dispersing the polyoxometallate compound in a solvent to form a second system, and then the first The system and the second system are uniformly mixed to form the composite ink.
  • the preparation method may include the following steps:
  • organic solvent 1 or the organic solvent 2 is selected from the group consisting of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ethylene glycol, and ethylene glycol monomethyl ether. Or a variety.
  • the selection of the solvent requires a combination of the dispersibility of the polyoxometallate compound in different solvents and the solvent requirements of the subsequent film deposition process.
  • the ink since the perovskite film is decomposed by water, the ink must be a water-free system, and the alcohol of butanol and propanol is also destructive to the perovskite film, so when the ink is disposed, PMA is required to be dispersed in anhydrous methanol, ethanol or methanol, ethanol and butanol mixed solvent.
  • PEDOT:PSS is also required to be dispersed in water. Therefore, PMA is dispersed in absolute ethanol and PEDOT:PSS is toluene phase system. .
  • the surface tension of the solvent can also be adjusted to improve the contact property of the ink with the substrate.
  • One aspect of the present invention also provides the use of the polymer-polyoxometal compound composite ink, for example, in the preparation of photovoltaic devices, particularly as an electrode interface modifying material.
  • One aspect of the present invention also provides a film which is mainly formed of the polymer-polyoxometal compound composite ink.
  • the polymer-polyoxometal compound compound provided by the present invention is uniformly dispersed in a solvent, in the film prepared by using the composite material of the present invention, a polymer and a polyoxometalate compound can be better. Mix to form a uniform composite film. At the same time, the polymer can be effectively filled in the space between the polyoxometal compound, so that the compactness and uniformity of the composite film can be improved, and the surface flatness of the composite film can be improved.
  • An aspect of the invention also provides a method of preparing the film, comprising: forming the film by applying or coating the polymer-polyoxometal compound composite ink onto a substrate by coating or printing.
  • the film may be directly deposited on the surface of the active layer or a plurality of functional film surfaces, which may include a light-emitting layer or a charge transport layer in an organic electroluminescent device, and light in an organic solar cell.
  • These functional films may include single or blended films of polymers or small molecules in terms of materials, inorganic films, organic-none Hybrid film of the machine.
  • the film of the present invention is deposited on the surface of the above functional film to prepare a conventional upright structure organic photoelectric device, and can also be used for preparing a laminated organic photoelectric device, such as a laminated OLED, a laminated organic solar cell, or a laminated calcium. Titanium ore solar cells.
  • the coating method may include, but is not limited to, a spin coating film, a knife coating, a slit coating, etc., and the printing methods include inkjet printing, screen printing, gravure printing, flexographic printing, and the like, but are not limited thereto. this.
  • the film of the present invention may also be deposited directly onto other various substrate surfaces, wherein the substrate material may include, but is not limited to, glass, plastic, paper, and foil, such as stainless steel, aluminum foil, and the like.
  • the film of the present invention may also be deposited on some transparent or opaque conductive film.
  • a transparent or opaque conductive film between the film of the present invention and the above-mentioned base material.
  • transparent conductive films include, but are not limited to, indium tin oxide (ITO) film, fluorine-doped tin oxide (FTO), metal grid line film, nano wire film, and the like.
  • the opaque conductive film includes a nano metal film prepared by a printing method or a metal or alloy nano film deposited by vacuum, such as an Al film, a Cu film, an Ag film, an Al:Mg alloy film, or the like, but is not limited thereto.
  • One aspect of the invention also provides for the use of the film, for example as a functional material or functional unit in some devices.
  • the device is a photovoltaic device having electro-optic and/or photo-electric conversion characteristics.
  • the film of the present invention can be applied as an electrode interface modifying material, for example, as an interface modification layer of an anode, which can effectively adjust the surface work function of the electrode and improve the interface contact between the electrode and the photoelectric active layer. performance.
  • Some typical optoelectronic devices may be, but are not limited to, solar cell devices or electroluminescent diode devices.
  • the dispersion/solution of the polyoxometal compound and the dispersion/solution of the polymer are mixed by different volume ratios to obtain a polymer-polyoxometal compound compound ink.
  • PMA molybdenum phosphate
  • PEDOT PSS composite ink
  • an aqueous dispersion of PMA isopropanol and PEDOT:PSS is mixed according to different volume ratios and obtained by ultrasonic dispersion.
  • the polymer-polyoxometal compound composite ink may be deposited on the surface of the ITO electrode or the organic photoactive layer by spin coating, knife coating or the like to form an anode modified layer.
  • a composite anode modification layer is spin coated on the surface of the organic active layer in an inverted structure organic optoelectronic device.
  • the composite anode modification layer is deposited directly on the transparent conductive electrode in a perovskite cell.
  • the composite anode modified layer and the conventional anode modified layer material pair Compared with the film, it exhibits better film-forming property and higher stability, and the material is cheap, the operation is simple, the experiment repeatability is good, and the organic photoelectric device can be better combined with printing in the process.
  • PEI ink preparation 10 mg of PEI solid was taken, about 3.3 mL of anhydrous methanol was added to a total mass of 2.5 g, and ultrasonication was dissolved to obtain a PEI ink having a weight concentration of 0.4%.
  • ZnO:PEI composite ink ZnO ink with a concentration of 10mg/mL and PEI ink with a weight concentration of 0.4% are mixed according to different volume ratios to adjust the weight ratio between the two, and the ultrasonic can be clarified and transparent.
  • ZnO: PEI composite ink ZnO ink with a concentration of 10mg/mL and PEI ink with a weight concentration of 0.4% are mixed according to different volume ratios to adjust the weight ratio between the two, and the ultrasonic can be clarified and transparent.
  • the structure of the inverted device includes ITO cathode, ZnO: PEI composite cathode modification layer, P3HT: PC 61 BM photoactive layer, MoO 3 anode modification layer, Al anode.
  • the device structure is ITO/ZnO: PEI/P3HT: PC 61 BM/MoO 3 /Al.
  • the ZnO:PEI composite cathode modified layer was spin-coated at 2300 rpm for 1 min, and annealed at 124 ° C for 10 min in a glove box.
  • Table 1 it can be seen that when the weight ratio of ZnO:PEI is between 25:3-25:7.5, the performance of the solar cell device does not change much, when the weight ratio of ZnO:PEI is increased to 25:12 and At 25:15, the short-circuit current and fill factor of the device are greatly reduced.
  • the S-curve curve appears on the JV curve of the device, indicating that the optimal weight ratio of ZnO:PEI is between 25:3-25:7.5, and the PEI is increased.
  • the effect of ZnO on the modified ITO electrode has been affected by the weight.
  • Inverted devices with ZnO, ZnO: PEI and PEI as cathode modification layers were respectively prepared by using ZnO, ZnO: PEI and PEI as cathodes, and used in inverted devices to compare the performance of three kinds of cathode modified layers.
  • Impact. ZnO ink, ZnO: PEI ink, PEI ink were spin-coated at 2300 rpm for 1 min, and then annealed at 124 ° C for 10 min in a glove box.
  • the three structures were respectively applied as a cathode modification layer to an inverted structure device having a structure of ITO/ETL/P3HT:PC 61 BM/MoO 3 /Al.
  • the device performance of the composite cathode modification layer with ZnO: PEI is better than that of the device with the PEI as the cathode modification layer, and compared with the device with ZnO as the cathode modification layer.
  • the overall performance of the device will not be reduced. From the AFM image of the film (Fig. 3), it can be seen that the combination of ZnO and PEI effectively reduces the agglomeration of ZnO nanoparticles.
  • the surface roughness of ZnO:PEI film is smaller than that of ZnO film.
  • the combination of ZnO and PEI in the appropriate weight ratio can not only effectively reduce the agglomeration of ZnO nanoparticles, and the device with the composite film as the cathode modification layer can be obtained as the cathode modification layer with the ZnO single layer.
  • the device has comparable performance.
  • Preparation of ZnO:PEIE composite ink Take ZnO ink with a concentration of 10 mg/ml (the preparation process can refer to Example 1) and a solution of PEIE (80% methoxylated polyethyleneimine) with a weight concentration of 0.4%. Different volume ratio Combined, ultrasonic dispersion to obtain ZnO:PEIE composite ink.
  • ZnO:PEIE composite cathode modified layer can be obtained by spin coating on the surface of ITO electrode at 2300 rpm.
  • the preparation process of the PMA: PEDOT:PSS composite ink includes:
  • PMA ink Take 1 mg of phosphomolybdic acid trihydrate (H 3 PO 4 ⁇ 12MoO 3 ⁇ 3H 2 O, PMA) powder, add 1 mL of re-distilled isopropanol, and ultrasonically to completely disperse, that is, the weight concentration is 1 mg/mL PMA ink.
  • PMA PEDOT: Preparation of PSS composite ink: PMA ink with concentration of 1mg/mL and PEDOT:PSS (Clevios PV P AI4083) ink are mixed according to different volume ratios, and PMA can be obtained by ultrasonic: PEDOT:PSS composite ink.
  • the corresponding PMA: PEDOT: PSS composite film preparation process comprises: coating the PMA: PEDOT: PSS composite ink on a base material by a general method such as spin coating or blade coating, and drying to form the composite film.
  • the composite film is absorbed in both the ultraviolet region and the near-infrared region, and the absorption of the near-infrared region is caused by the absorption of PEDOT:PSS.
  • the absorption spectrum of P3HT:PC 61 BM film before and after deposition of PMA:PEDOT:PSS can be confirmed to confirm that the composite film can be deposited on the surface of the active layer.
  • the preparation process of the inverted device with the PMA:PEDOT:PSS composite film as the anode modification layer comprises: the structure of the inverted device comprises an ITO cathode, a ZnO cathode modification layer, a PTB7: PC 61 BM photoactive layer, PMA: PEDOT: PSS anode modification layer, Al anode.
  • Inverted structural devices with ITO/ZnO/PTB7:PC 61 BM/anode modified layer/Al were prepared by using PMA, PEDOT:PSS, PMA:PEDOT:PSS, and vapor-deposited MoO 3 as anode modification layers.
  • PMA ink, PMA: PEDOT: PSS ink, PEDOT ink was spin-coated at 2300 rpm for 1 min, and then annealed at 124 ° C for 10 min in a glove box.
  • PTB7 PC 61 BM film with an island size of about 100 nm, which is mainly agglomeration from PMA, thus making PTB7:
  • the roughness of the PC 61 BM film was increased from 1.7 nm to 4.1 nm.
  • PMA and PEDOT:PSS are combined to improve the agglomeration of PMA particles, so that the roughness of PMA:PEDOT:PSS film is 2.1 nm.
  • the device performance of the composite anode modified layer with PMA:PEDOT:PSS is better than that of the device with the PMA alone as the anode modified layer, compared to the PMA.
  • the open circuit voltage and short circuit current of the device are obviously improved, and the overall device efficiency is improved by about 20%.
  • the PMA:PEDOT:PSS composite film is used as the anode modification layer, and the obtained device has better stability in long-term operation than pure PEDOT:PSS, pure PMA, and e-MoO. 3 reference device.
  • the preparation process of the PMA: PEDOT:PSS composite ink includes:
  • PMA ink Take x mg of phosphomolybdic acid trihydrate (H 3 PO 4 ⁇ 12MoO 3 ⁇ 3H 2 O, PMA) powder, add 1 mL of isopropanol, and ultrasonically to completely disperse to obtain a weight concentration of x. Mg/mL PMA ink.
  • PMA PEDOT: Preparation of PSS composite ink: PMA ink and PEDOT:PSS (AI4083) ink are mixed in a volume ratio of 10:1, and a series of PMA: PEDOT:PSS composite ink can be obtained by ultrasonication.
  • the structure of the perovskite battery in this embodiment is: ITO/PMA: PEDOT: PSS/PVSK/PCBM/Al, wherein The pure PEDOT:PSS modified layer is also used as a reference device.
  • Table 3 gives the performance parameters of the device. It can be seen that the device performance obtained by using the PMA:PEDOT:PSS composite as the anode modification layer is similar to that of the device containing pure PEDOT:PSS, indicating that the PMA:PEDOT:PSS composite layer can be used as the anode modification layer of the perovskite battery.
  • Example 5 phosphotungstic acid (H 3 PW 12 O 40 , PWA): application of benzenesulfonic acid (PSS) composite interfacial layer in organic solar cells
  • Example 6 Application of a composite interface layer based on silicomolybdic acid (SMA): polymer in perovskite solar cells (PVSK)
  • silicomolybdic acid Preparation of silicomolybdic acid: composite ink: 30mg of silicomolybdic acid (SiMo 12 O 40 ) is dissolved in 1mL of methanol, and a polyanthracene derivative (CPE-K) methanol ink with a solubility of 3mg/mL is disposed, and the silicon molybdenum is prepared.
  • the acid and polyfluorene ink were combined in a certain ratio to obtain a composite ink having a total concentration of 20 mg/mL.
  • the ink can be prepared by a plurality of methods such as spin coating to obtain a composite interface layer film.
  • Example 7 Phosphomolybdic acid amine (PMN): application of composite interfacial layer in organic solar cells
  • polyvinylpyrrolidone PVP
  • phosphomolybdic acid amine (NH 4 ) 6 PMo 18 O 62 , PMN)
  • the composite ink (PMN: PPV) based on phosphomolybdic acid amine and polyvinylpyrrolidone was obtained by mixing at a weight ratio of 1:10.
  • Example 8 Application of a tungsten polyacid (WA) composite interfacial layer in an organic solar cell
  • Example 9 Phosphotungstic acid (H 3 PW 12 O 40 , PWA) composite interfacial layer: application of PEI composite as cathode interface layer in organic solar cells
  • PEI composite layer PEDOT:PSS
  • PffBT4T2OD PC 61 BM active layer
  • PWA PEI composite layer

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Abstract

一种聚合物-金属化合物复合墨水及其制备方法与应用。其中所述复合墨水包含：至少一种聚合物；至少一种金属化合物材料，所述金属化合物材料选自多金属氧簇化合物和纳米金属氧化物；至少一种溶剂，用于与所述复合墨水中的其余组分配合而形成均匀流体状分散体系。同时还公开了所述复合墨水的制备方法。所述复合墨水原料来源广泛，易于制备，成本低廉，并且可以被通过旋涂、印刷等方式制成复合薄膜，该复合薄膜可以作为电极修饰层应用于太阳能电池、发光二极管等光电器件，以改善电极和有机活性层之间的接触性能，进而提高光电器件的性能和良品率。

Description

聚合物-金属化合物复合墨水及其制备方法与应用 发明领域
本发明具体涉及一种聚合物-金属化合物复合墨水，其制备方法及应用，例如在光电器件中的应用，属于光电半导体材料与器件领域。
背景技术
相较于传统的无机光电器件，基于有机半导体材料的新型可溶液法加工的光电器件，如：有机太阳能电池、钙钛矿太阳能电池、有机电致发光二极管(OLED)等具有成本低、轻柔、易大面积卷对卷生产等优势，具有非常广阔的应用前景。这类新型光电转换器件通常具有三明治式多层结构，包括有源层和电极，所述电极包括阴极和阳极。其中，电极主要是完成电子或空穴的注入(如电致发光器件)或收集(太阳能电池器件)过程。在很多情况下，电极与光电活性层之间功函数并不匹配，存在界面势垒，影响了电子或空穴的注入或收集效率，进而影响了器件性能。通过在电极与有源层之间引入界面修饰层可以调节电极表面功函数，使得电极与光电活性层之间形成欧姆接触，从而降低电子的注入或收集效率，达到提高器件性能的目的。
目前，常用的电极修饰材料包括两大类：金属氧化物和聚合物类。金属氧化物，如：氧化锌、氧化钛、氧化锡等(尤其适用于阴极修饰)和氧化钼、氧化矾、氧化镍等(尤其适用于阳极修饰)具有导电性能好、材料稳定性高等优点，是优良的电极界面修饰材料。但传统的金属氧化物薄膜多采用真空溅射方法沉积，与基于油墨的印刷方法不兼容。采用溶液的方法制备各种纳米粒子，可以满足溶液法加工有机光电器件的要求。将金属氧化物的颗粒尺寸下降到纳米尺度，如：3-50纳米，特别是下降到5-15纳米左右时，金属纳米颗粒可以分散在溶剂之中，从而满足溶液法加工制备。例如，有报道利用溶液法制备氧化锌纳米粒子(ZnO)、氧化钛纳米粒子(TiO2)及铯掺杂的氧化钛纳米粒子(TiO2:Cs)、氧化钼纳米粒子(MoO3)、氧化矾(V2O5)纳米粒子、氧化镍(NiO)纳米粒子作为电极修饰层有效提高了有机太阳能电池的器件效率及器件的稳定性【例如可参阅Adv.Mater.2012,24(38),5267-5272】。但纳米微粒分散液在印刷制备薄膜过程中容易发生纳米颗粒的团聚，造成薄膜表面缺陷较多，且刚性易断裂，易导致器件性能下降甚至短路(参见ACS Appl.Mater.Interfaces 2014,6(20),18172-18179)。此外，单纯的 金属氧化物的能带结构由材料制备过程所决定，后期调整比较困难，因而实际应用过程中受到了一定的限制。
就聚合物而言，用于阳极修饰层的主要是3,4-乙撑二氧噻吩聚合物-聚苯乙烯磺酸盐，即(PEDOT:PSS)导电聚合物，其具有导电性高、成膜质量高等优点，但是在有机薄膜层上沉积PEDOT:PSS通常需要在PEDOT:PSS中添加表面活性剂对其进行改性或者通过对有机活性层进行表面处理降低其表面能。然而表面活性剂的后期去除比较困难。以等离子体或者紫外臭氧处理有机活性层表面，对设备要求也较高，且将有可能一定程度破坏有机物薄膜，缩短器件寿命。用于阴极修饰的聚合物材料，通常是指离子型的共轭聚合物，如：聚芴、聚噻吩、聚咔唑及其它们的衍生物，或者非共轭聚合物，如聚乙酰亚胺等衍生物。。但这类基于共轭聚合物材料的离子型聚合物电解质的合成制备方法较为复杂，材料成本较高。另外一类用于阴极界面修饰的是非共轭聚合物(例如参阅Science 2012,336(6079),327-332)。相比于共轭聚合物电解质，这类非共轭聚合物是商业上成熟的聚合物，可以大规模制备，具有成本低，技术成熟等优点。但是由于聚合物的导电性较差，在利用聚合物作为电极界面修饰层时，器件性能表现出非常强烈的薄膜厚度依赖性，即器件性能对电极界面修饰层的厚度非常敏感，最优厚度通常在10-15纳米之间，给器件制备工艺带来了很大的难度。
利用金属氧化物纳米粒子/导电聚合物双层结构作为电极修饰层，即在电极表面先沉积一层金属氧化物纳米粒子薄膜，然后在此基础上再沉积一层共轭聚合物聚电解质薄膜的方法可以在一定程度上解决金属纳米粒子涂层的不均匀性的问题。但这一方法在沉积第一金属氧化物薄膜的过程中仍然存在纳米金属氧化物颗粒的团聚问题；此外，这一方法也增加了电极修饰界面数，增加了器件性能的影响因素，于此同时也使得器件的制备工艺变得更为复杂。
又及，近期报道的纳米团簇也具有修饰功函数的作用，与金属氧化物纳米粒子相比，该类纳米团簇材料具有材料廉价、墨水配置简单、溶解性好，可溶液方法加工的优点。多金属氧簇可以作为阳极的界面修饰层，例如一些文献报道的磷钼酸(PMA)可以作为倒置结构的有机太阳能电池中的阳极缓冲层。作为PTB7:PC71BM器件的阳极缓冲层，可以得到8.3％高效率的器件性能。此外，多金属氧簇也可以作为阴极界面修饰层，例如，文献报道H3PW12O40可作为发光二极管和有机太阳能电池的阴极缓冲层。但是该类材料也存在着团聚现象严重，薄膜粗糙度大的问题。
发明内容
本发明的主要目的在于提供一种聚合物-金属化合物复合墨水及其制备方法，该聚合物-金属化合物复合墨水可用于电极界面修饰，并可以实现对电极的表面功函的调整，从而克服现有技术中的不足。
为实现前述发明目的，本发明采用的技术方案包括：
本发明实施例提供了一种聚合物-金属化合物复合墨水，其包含：
至少一种聚合物，
至少一种金属化合物材料，所述金属化合物材料选自多金属氧簇化合物和纳米金属氧化物，以及，
至少一种溶剂，用于与所述复合材料中的其余组分配合而形成均匀流体状分散体系。
在一些实施方案中，所述金属化合物材料选自多金属氧簇化合物。
进一步的，所述聚合物包括共轭聚合物和/或非共轭聚合物。
在一些实施方案中，所述的聚合物-金属化合物复合墨水包含：
至少一种具有脂肪胺单元的聚合物，
至少一种纳米金属氧化物，
用作所述溶剂的至少一种有机醇。
进一步的，所述纳米金属氧化物包含选自下列元素组的金属元素：钼、钒、钨、镍、钛、锡、锌。
进一步的，所述纳米金属氧化物还可包含不同于所述元素组中的任一金属元素及氧元素的金属和/或非金属元素。
本发明实施例还提供了一种制备所述聚合物-金属化合物复合墨水的方法，其包括：将所述聚合物与所述金属化合物材料于溶剂中均匀混合而形成所述复合墨水。
本发明实施例还提供了一种薄膜，其主要由所述的聚合物-金属化合物复合墨水形成。
本发明实施例还提供了一种薄膜的制备方法，其包括：通过涂布或印刷方式将所述的聚合物-金属化合物复合墨水施加到基底上而形成所述薄膜。
本发明实施例还提供了一种装置，其包含所述的薄膜。
与现有技术相比，本发明的优点包括：
1)本发明的聚合物-金属化合物复合墨水及薄膜原料来源广泛，易于制备，成本低廉；
2)利用本发明的聚合物-金属化合物复合墨水形成的薄膜作为界面修饰材料可以提 高界面修饰层的薄膜致密性，降低界面修饰层的表面粗糙度，从而提高器件的性能，例如，在应用于电极界面修饰时还可实现对电极的表面功函调整；
3)本发明的聚合物-金属化合物复合墨水可以通过旋转涂布、刮刀涂布、喷墨打印等多种常见方式沉积形成薄膜，具有加工工艺简单等优势；
4)当应用本发明的聚合物-金属化合物复合墨水物作为界面修饰材料时，形成的器件性能表现出更低的薄膜厚度依赖性，从而能够降低对器件制备的工艺要求，有利于提高器件的良品率。
附图说明
图1是实施例1中一种太阳能电池器件的结构示意图；
图2是实施例1中以ZnO、ZnO:PEI、PEI作为阴极修饰层的P3HT:PC61BM体系太阳能电池的J-V曲线图；
图3a-图3b分别是实施例1中ZnO薄膜、ZnO:PEI薄膜的AFM图。
图4是实施例3中一种太阳能电池的结构示意图。
图5a是实施例3中PMA、PEDOT:PSS、PMA:PEDOT:PSS薄膜的吸收光谱图。
图5b是实施例3中在P3HT:PC61BM上分别沉积PEDOT:PSS、PMA:PEDOT:PSS的吸收光谱图。
图6a-图6c分别是实施例3中PTB7:PC61BM薄膜、PTB7:PC61BM/PMA薄膜、PTB7:PC61BM/PMA:PEDOT:PSS薄膜的AFM图。
图7a-图7b是实施例3中以PMA、PEDOT:PSS、PMA:PEDOT:PSS、蒸镀MoO3(e-MoO3)作为阳极修饰层的PTB7:PC61BM体系太阳能电池的J-V曲线图。
图8a-图8d是以PMA、PEDOT:PSS、PMA:PEDOT:PSS、蒸镀MoO3(e-MoO3)作为阳极修饰层的倒置结构器件的稳定性测试图。
图9是实施例5中所获器件的J-V曲线。
具体实施方式
针对现有技术的诸多缺陷，本案发明人经长期研究和大量实践，提出了本发明的技术方案，下文将对其作更为详尽的解释说明。但是，应当理解，在本发明范围内，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
本发明的一个方面于一些实施例提供了一种聚合物-金属化合物复合墨水，其包含：
至少一种聚合物，
至少一种金属化合物材料，所述金属化合物材料选自多金属氧簇化合物和纳米金属氧化物，以及，
至少一种溶剂，用于与所述复合墨水中的其余组分配合而形成均匀流体状分散体系。
在第一个实施方案中，所述聚合物-金属化合物复合墨水为聚合物-纳米金属氧化物复合墨水，其包含：
至少一种具有脂肪胺单元的聚合物，
至少一种纳米金属氧化物，
用作溶剂的至少一种有机醇。
本发明的第一个实施方案所提供的墨水中，聚合物能够有效填充在金属氧化物纳米微粒之间的空隙之中，从而提高复合物薄膜的致密性以及均匀性，降低电极界面修饰层表面的粗糙度。与此同时，所述墨水配方中聚合物所含有的脂肪胺单元能够调节金属氧化合物的功函、降低薄膜中的金属氧化物的表面缺陷密度，提高载流子浓度以及载流子迁移率等，从而调节聚合物-纳米金属氧化物薄膜对电极界面的修饰性能，进而改变光电器件的应用性能。
所述的脂肪胺单元包括一级、二级或三级脂肪胺，即分子中含有如下分子结构单元中的一种：
Figure PCTCN2015097676-appb-000001
式中，m、n、p独立地选自1-12的整数。
所述的“含有”表示分子中含有至少一个上述的结构单元。而上述的结构单元可以是在聚合物分子的主链上，也可以是在聚合物分子的侧链上，也可以是同时在分子的主链及侧链上都含有上述的脂肪胺结构单元。
优选地，本发明所提供的含有脂肪胺单元的聚合物选自直链或支化的聚乙烯亚胺、端位乙氧基化或乙胺基化的聚乙烯亚胺、含聚乙烯亚胺片段的共聚物、或上述聚合物的混合物。上述的直链或支化的聚乙烯亚胺、端位乙氧基化或乙胺基化的聚乙烯亚胺、以及在此基础上构建的含有聚乙烯亚胺片段的共聚物是工业上非常成熟的化学产品，具有材料制备工艺成熟，产品性能稳定等优点，是实现本发明解决方案的一个优选方式。除 此之外，上述聚合物的任意比混合物也可以适用于本发明的解决方案。
其中，所述纳米金属氧化物也可选自但不限于含有锌、钛、钼、钒、钨、镍等元素的氧化物以及其他元素掺杂的这些氧化物。例如：ZnO，Al:ZnO，Mg:ZnO，Ca:ZnO，Ga:ZnO，In:ZnO，Ga,In:ZnO，F:ZnO，N:ZnO，TiO2，Y:TiO2，Yb:TiO2，Co:TiO2，S:TiO2，SnO2，In:SnO2，Ga:SnO2，Zn:SnO2，MoO3，P:MoO3，Nb:MoO3，Ti:MoO3，In:MoO3，V2O5，Sn:V2O5，Mo:V2O5，Mn:V2O5，Cu:V2O5，WO3，Fe:WO3，Co:WO3，Ni:WO3，Cu:WO3，Zn:WO3，Nb:WO3，Mo:WO3，NiO，Li:NiO，V:NiO，Mn:NiO，Al:NiO，Fe:NiO，Ti:NiO，N:NiO，除此之外，金属氧化物或者元素掺杂的金属氧化物的混合物也适用于本发明的解决方案。其中，所述纳米金属氧化物优选为氧化锌、氧化锡、氧化钛以及其掺杂的金属氧化物。
进一步的，为了保证纳米金属氧化物在有机溶剂中的良好分散性能，所述的纳米金属氧化物的颗粒大小通常为3-50nm，更优选为5-15nm。
其中，所述溶剂优选为有机溶剂，其中至少含有一种有机醇。在复合墨水添加有机醇，可以能够保证纳米金属氧化物颗粒不发生明显的团聚，从而有效稳定所配制的墨水。所述的有机醇选自但不限于：甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、乙二醇、乙二醇单甲醚。此外，也可以选用由上述两种或两种以上的有机醇进行混合形成的混合醇溶剂来稳定纳米金属氧化物颗粒。
在其它的一些实施方案中，本发明的溶剂中还可包括辅助有机溶剂，其可选自但不限于丙酮、氯仿、甲苯、二甲苯、三甲苯、氯苯、二氯苯中的一种或两种以上，用于分散及稳定所配置的复合墨水，调节复合墨水的表面张力，提高所配置复合墨水的成膜性能。
较为优选的，本发明的复合墨水中聚合物-金属氧化物纳米微粒的重量/体积浓度为0.5-60mg/mL。更低的固含量使得复合物加工制备薄膜过程中复合物沉积量不足，更高的固含量浓度容易导致固体析出。
较为优选的，在本发明的复合墨水中，聚合物与纳米金属氧化物的重量混合比为1:25-1:2.5之间，过高的聚合物将弱化金属氧化物在提高修饰层稳定性方面的作用，过低的聚合物比例则难以均匀分散纳米金属氧化物颗粒，导致无法形成致密的复合薄膜。更为优选的比例为1:6-1:4之间。
一种制备所述聚合物-纳米金属氧化物复合墨水的方法包括：将纳米金属氧化物的分散液与所述聚合物的溶液混合，形成所述复合墨水。
进一步的，该制备方法可以包括如下步骤：
(a)将所述聚合物溶解于有机溶剂1中，形成聚合物溶液；
(b)将所述纳米金属氧化物颗粒均匀分散于有机溶剂2中，形成纳米金属氧化物分散液；
(c)将所述聚合物溶液与所述纳米金属氧化物分散液按照不同的比例混合均匀。
其中，所述有机溶剂1或有机溶剂2至少选自于甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、乙二醇、乙二醇单甲醚中的一种或多种。
在本发明的复合墨水中，溶剂的选择需要结合纳米金属氧化物在不同溶剂中的分散性能以及后续薄膜沉积过程对溶剂的要求进行综合选择。以制备结构为ITO/PEDOT:PSS/P3HT:PC61BM/ZnO:PEI/Al的正置的有机太阳能电池为例，为了避免旋涂阴极修饰层ZnO:PEI过程中溶剂对光学活性层P3HT:PC61BM，溶剂需避免使用氯苯、二氯苯等溶剂。因此ZnO纳米颗粒选择溶解在氯仿溶剂中，而PEI则溶解在甲醇中，然后对二者进行混合配置。而在制备结构为ITO/ZnO:PEI/P3HT:PC61BM/MoO3/Al的倒置结构有机太阳能电池时，由于ZnO:PEI是直接在ITO表面进行制备，因此不存在溶剂对底层材料的破坏问题，也因此可以根据印刷工艺的需求，选择正丁醇或者氯苯等进行配置。
此外，溶剂比例的不同，还可以调整溶剂的表面张力，从而改善墨水与基底的接触性能。
本发明还提供了所述聚合物-纳米金属氧化物复合墨水于制备光电器件中的应用。
作为其中的典型应用方式之一，本发明提供了一种聚合物-纳米金属氧化物复合薄膜，其主要由所述聚合物-纳米金属氧化物复合墨水形成，其中采用的成膜方式包括涂布或印刷方式等。
在实际的沉积制备过程中，所述聚合物-纳米金属氧化物符合薄膜通常沉积在基底材料之上。所述基底材料可以包括但不限于：玻璃、塑料、纸张以及金属薄片，如：不锈钢、铝箔等。所述涂布方式可以包括但不限于旋转涂膜、刮刀涂布、狭缝涂布等；所述的印刷方式包括喷墨印刷、丝网印刷、凹版印刷、柔版转印等。
在实际应用过程中，本发明的聚合物-纳米金属氧化物复合薄膜还可以沉积在一些透明或不透明的导电薄膜之上。换句话说，本发明的复合薄膜与上述的基底材料之间还可以有一层透明或不透明的导电薄膜。透明的导电薄膜包括：氧化铟锡(ITO)薄膜、氟掺杂氧化锡(FTO)、金属栅线网格薄膜、纳米金属线薄膜等；不透明的导电薄膜包括：印刷方法制备的纳米金属薄膜或者由真空沉积的金属或合金纳米薄膜，如：Al膜、Al:Mg合金薄膜等。
在另外一些应用实例中，本发明提供的聚合物-纳米金属氧化物复合薄膜还可以沉积 在功能薄膜表面。这些功能薄膜表面包括有机电致发光器件中的发光层或电荷传输层、有机太阳能电池中的光活性层或电荷传输层、或钙钛矿太阳能电池中的钙钛矿晶体层或电荷传输层。将本发明所提供的聚合物-纳米金属氧化物复合薄膜沉积在上述的功能薄膜表面可以制备传统的正置型有机光电器件，也可以用于制备叠层有机光电器件，如叠层OLED，叠层有机太阳能电池，或叠层钙钛矿太阳能电池。
更进一步地，本发明公布了一种聚合物-纳米金属氧化物复合薄膜在光电器件中的用途。其中，本发明的聚合物-纳米金属氧化物复合薄膜可以有效调节电极的表面功函，改善电极与光电活性层之间的界面接触性能。因此，本发明的复合薄膜可以用于具有光电转换特性的电子器件中，例如，作为阴极的电极界面修饰层。
典型的光电器件，是指那些具有电-光和/或光-电转换特性的光电器件，例如，太阳能电池器件或电致发光二极管器件等，但不限于此。
例如，在本发明的一典型实施案例之中，本发明的技术路线可以概括为：
纳米金属氧化物颗粒合成：
1)以ZnO纳米颗粒的合成为例：以锌盐作为原料，磁力搅拌溶解于无水甲醇中，加热至60～65℃，逐滴加入KOH的甲醇溶液，60℃恒温加热搅拌2h，得到ZnO纳米颗粒。
2)反应所得到的纳米颗粒经过静置-清洗沉淀-离心-超声分散多步处理，最后得到醇分散的ZnO纳米颗粒分散液。具体操作：反应液静置3h，移出上清液，在下层沉淀中加入一定量甲醇搅拌10min，静置过夜后移出上清液，加入一定量甲醇于沉淀中，4000rpm离心10min，除去上清液，保留下层白色沉淀即为纳米ZnO颗粒，以三氯甲烷-甲醇混合溶剂超声分散即得到纳米ZnO颗粒分散液。
聚合物-纳米金属氧化物的制备：
纳米金属氧化物颗粒分散液和聚合物的分散液通过不同体积比进行混合即得到聚合物-纳米金属氧化物复合墨水。以ZnO:PEI复合墨水为例：ZnO分散液与PEI分散液按照不同体积比混合，经过超声分散即得。
聚合物-纳米金属氧化物阴极修饰层的制备：
聚合物-纳米金属氧化物复合墨水可以通过旋涂、刮涂等方法在ITO电极或有机光活性层表面沉积得到阴极修饰层。一些实例中在倒置结构有机光电器件中在阴极表面旋涂沉积复合阴极修饰层。
由本发明工艺制备的纳米金属氧化物-导电聚合物组合物作为有机光电器件的阴极修饰层，与传统阴极修饰层材料对比，有更好的成膜性和更高的稳定性，且操作简单，实验重复性好，在工艺上可以更好的结合印刷制备有机光电器件。
第二个实施方案中，所述聚合物-金属化合物复合墨水为聚合物-多金属氧簇化合物复合墨水，其包含：
至少一种聚合物，
至少一种多金属氧簇化合物，以及，
至少一种溶剂，用于与所述复合墨水中的其余组分配合而形成均匀分散体系。
较佳的，所述复合材料为流体状均匀分散体系，特别是均匀液相分散体系，因此可以被认为是一种聚合物-多金属氧簇化合物墨水。
本发明的第二个实施方案所提供的墨水中，通过将聚合物与多金属氧簇化合物之间均匀混合，可降低多金属氧簇化合物的团聚现象，提高成膜均匀性，同时聚合物能够有效填充在多金属氧簇化合物之间的空隙中，故而可以提高复合物薄膜的致密性以及均匀性，降低界面修饰层表面的粗糙度。于此同时，聚合物在复合界面层中也可起到调节多金属氧簇化合物的功函数，进而改变光电器件的应用性能的功能。
在一些实施例中，所述的聚合物可以包括聚苯胺、聚噻吩、聚吡咯、聚硒吩、聚芴及其衍生物等共轭聚合物，或者聚磺酸、聚对甲苯磺酸等非共轭聚合物中任一种或两种以上的组合但不限于此。
在一些较为典型的实施例中，所述聚合物可以为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS)，可用于有机以及有机/无机复合光电器件中。
在一些实施例中，所述的多金属氧簇化合物可以选自含有金属钼、钨、钒中的任意一种或者多种的多金属氧簇化合物，但不限于此。
进一步地，所述多金属氧簇化合物中还可含有磷、硅、锗或砷等元素，但不限于此。
在一些较为典型的实施例中，所述的多金属氧簇化合物可以包括Keggin型多金属氧簇化合物，如：[BM12O40]n-、[PM12O40]n-、[SiM12O40]n-、[GeM12O40]n-、[AsM12O40]n-、[AlM12O40]n-(M为金属钼、钨或钒，n是正整数)，或者Wells-Dawson型多金属氧簇化合物，如：[P2M18O62]n-，[As2M18]n-(M为金属钼、钨，n是正整数)，Lindqvist型多金属氧簇化合物，如：[Mo6O19]2-、[W6O19]2-以及多钼酸([Mo8O26]2-)或多钨酸([W10O32]4-)基化合物等，但不限于此。
进一步的，在一些较为具体的实施例中，所述多金属氧簇化合物可以是金属多酸或者金属多酸的盐，如铵盐、钠盐、钾盐等。
进一步的，在所述聚合物-多金属氧簇化合物复合墨水中，聚合物与多金属氧簇化合物的重量比优选为1:0.1-1:15，尤其优选为1:1-1:3，进一步优选为约1:1左右。过高的聚合物用量比例将弱化纳米材料在提高修饰层稳定性方面的作用，过低的聚合物用量比例 则难以均匀分散纳米材料，导致无法形成致密的复合薄膜。
在所述聚合物-多金属氧簇化合物复合墨水中，所述溶剂主要是为了便于分散聚合物及多金属氧簇化合物，特别是形成墨水。所述溶剂可选自水、有机醇或者水与有机醇形成的混合物等。优选的，通过添加有机醇，可以有效稳定所述墨水，且提高所述墨水在有机薄膜上的浸润性。其中，所述的有机醇可选自但不限于：甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、乙二醇、乙二醇单甲醚等。此外，也可以选用由两种以上的上述有机醇进行混合形成的混合醇溶剂来稳定无机纳米团簇颗粒。
在一些实施例中，所述溶剂中还可包括辅助有机溶剂，其可选自但不限于丙酮、氯仿、甲苯、二甲苯、三甲苯、氯苯、二氯苯中的任一种或两种以上，主要用于分散及稳定所述墨水，调节所述墨水的表面张力，提高所述墨水的成膜性能。
在一些较佳实施例中，所述聚合物-多金属氧簇化合物复合墨水中，聚合物-多金属氧簇化合物复合物的重量/体积浓度为0.5-20mg/mL，优选为3-8mg/mL。更低的固含量将使得以所述复合材料加工制备薄膜过程中复合物沉积量不足，更高的固含量浓度容易导致固体析出。
在一些实施例中还可将所述的聚合物-多金属氧簇化合物复合墨水与其它墨水组合而形成复合墨水。
本发明的一个方面还提供了一种制聚合物-多金属氧簇化合物复合墨水的方法，包括：将聚合物与多金属氧簇化合物于溶剂中均匀混合而形成所述复合墨水。
在一些实施例中，所述制备方法包括：将聚合物溶于和/或分散于溶剂中形成第一体系，以及将多金属氧簇化合物分散于溶剂中形成第二体系，再将该第一体系和第二体系均匀混合，从而形成所述复合墨水。
例如，在一些较为具体实施方案中，所述制备方法可以包括如下步骤：
(a)将所述聚合物溶解于溶剂1中，形成聚合物溶液；
(b)将所述多金属氧簇化合物均匀分散于溶剂2中，形成多金属氧簇化合物分散液或溶液；
(c)将所述聚合物溶液与所述多金属氧簇化合物分散液或溶液按照不同的比例混合均匀。
其中，所述有机溶剂1或有机溶剂2选自于水、甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、乙二醇、乙二醇单甲醚中的一种或多种。
在本发明的聚合物-多金属氧簇化合物复合墨水中，溶剂的选择需要结合多金属氧簇化合物在不同溶剂中的分散性能以及后续薄膜沉积过程对溶剂的要求进行综合选择。
例如，在制备结构为ITO/ZnO/PTB7:PC61BM/PMA:PEDOT:PSS/Al的正置的有机太阳能电池时，为了避免旋涂阳极修饰层PMA:PEDOT:PSS过程中溶剂对光学活性层的破坏，溶剂需避免使用氯苯、二氯苯等溶剂。因此钼磷酸(PMA)选择分散在异丙醇溶剂中，同时由于商业化的PEDOT:PSS为分散在水中，所以需要对醇和水的比例进行调整，使得所述墨水具有较高的稳定性，同时可以在有机层沉积获得均匀致密的薄膜。
又例如，在制备结构为ITO/TiO2/PVSK(CH3NH3PbX3,NH2CH＝NH2PbX3,X＝Cl、Br或I)/PMA:PEDOT:PSS/Al的钙钛矿电池时，由于钙钛矿薄膜遇水分解，故所述墨水必须是无水体系，且丁醇，丙醇类的醇对钙钛矿薄膜也有一定的破坏性，所以在配置所述墨水时除了要求PMA分散在无水甲醇、乙醇或甲醇、乙醇与丁醇混合溶剂之外，也要求PEDOT:PSS不能分散于水中，所以该体系中PMA分散在无水乙醇中，PEDOT:PSS为甲苯相体系。
再例如，在结构为ITO/PMA:PEDOT:PSS/PVSK(CH3NH3PbX3,NH2CH＝NH2PbX3,X＝Cl、Br或I)/PCBM/Al或者ITO/PMA:PEDOT:PSS/PTB7:PC61BM/MoO3/Al的体系中，因为PMA:PEDOT:PSS直接在ITO(氧化铟锡)表面进行制备，因此不存在溶剂对底层材料的破坏问题，也因此可以根据印刷工艺的需求以及墨水的稳定性，选择多种溶剂。
此外，溶剂比例的不同，还可以调整溶剂的表面张力，从而改善所述墨水与基底的接触性能。
本发明的一个方面还提供了所述聚合物-多金属氧簇化合物复合墨水的用途，例如在制备光电器件中的用途，特别是作为电极界面修饰材料的用途。
本发明的一个方面还提供了一种薄膜，其主要由所述的聚合物-多金属氧簇化合物复合墨水形成。
由于本发明所提供的聚合物-多金属氧簇化合物复合物均匀分散在溶剂中，因此，利用本发明的复合材料所制备的薄膜中，聚合物与多金属氧簇化合物之间能够较好地混合形成均匀的复合薄膜。同时聚合物能够有效填充在多金属氧簇化合物之间的空隙之中，故可以提高复合物薄膜的致密性以及均匀性，提高复合薄膜的表面平整度。
本发明的一个方面还提供了一种制备所述薄膜的方法，其包括：通过涂布或印刷方式将所述的聚合物-多金属氧簇化合物复合墨水施加到基底上而形成所述薄膜。
在实际的沉积制备过程中，所述的薄膜可以直接沉积在有源层表面或者多种功能薄膜表面，其可包括有机电致发光器件中的发光层或电荷传输层、有机太阳能电池中的光活性层或电荷传输层、或钙钛矿太阳能电池中的钙钛矿晶体层或电荷传输层等。这些功能薄膜就材料而言可以包括聚合物或者小分子的单一或者共混薄膜，无机薄膜、有机-无 机的杂化薄膜等。将本发明的所述薄膜沉积在上述功能薄膜表面可以制备传统的正置结构有机光电器件，也可以用于制备叠层有机光电器件，如叠层OLED，叠层有机太阳能电池，或叠层钙钛矿太阳能电池。所述涂布方式可以包括但不限于旋转涂膜、刮刀涂布、狭缝涂布等，所述印刷方式包括喷墨印刷、丝网印刷、凹版印刷、柔版转印等，但均不限于此。
在一些实施例中，本发明的所述薄膜也可以直接沉积在其它各种基底表面，其中所述基底材料可以包括但不限于：玻璃、塑料、纸张以及金属薄片，如：不锈钢、铝箔等。
在一些实施例中，本发明的所述薄膜还可以沉积在一些透明或不透明的导电薄膜之上。或者，也可以认为，本发明的所述薄膜与上述的基底材料之间还可以有一层透明或不透明的导电薄膜。这些透明的导电薄膜包括：氧化铟锡(ITO)薄膜、氟掺杂氧化锡(FTO)、金属栅线网格薄膜、纳米金属线薄膜等，但不限于此。这些不透明的导电薄膜包括：印刷方法制备的纳米金属薄膜或者由真空沉积的金属或合金纳米薄膜，如：Al膜、Cu膜、Ag膜、Al:Mg合金薄膜等，但不限于此。
本发明的一个方面还提供了所述薄膜的用途，例如作为功能材料或功能单元在一些装置中的应用。
优选的，所述装置为具有电-光和/或光-电转换特性的光电器件。
在一些实施例中，本发明的所述薄膜可应用为电极界面修饰材料，例如，作为阳极的界面修饰层，其可以有效调节电极的表面功函，改善电极与光电活性层之间的界面接触性能。
一些典型的光电器件可以是太阳能电池器件或电致发光二极管器件等，但不限于此。
进一步的，本发明的一典型实施案例的实施过程可以概括为：
1)聚合物-多金属氧簇化合物复合墨水的制备：
多金属氧簇化合物的分散液/溶液和聚合物的分散液/溶液通过不同体积比进行混合即得到聚合物-多金属氧簇化合物复合墨水。以钼磷酸(PMA):PEDOT:PSS复合墨水为例：PMA的异丙醇分散液与PEDOT:PSS的水分散液按照不同体积比混合，经过超声分散即得。
2)聚合物-多金属氧簇化合物复合修饰层的制备：
所述聚合物-多金属氧簇化合物复合墨水可以通过旋涂、刮涂等方法在ITO电极或有机光活性层表面沉积形成阳极修饰层。例如，在一些实施例中在倒置结构有机光电器件中在有机活性层表面旋涂沉积复合阳极修饰层。而在另一些实施例中在钙钛矿电池中在透明导电极上直接沉积该复合阳极修饰层。该复合阳极修饰层与传统阳极修饰层材料对 比，表现出更好的成膜性和更高的稳定性，而且材料廉价、操作简单，实验重复性好，在工艺上可以更好的结合印刷制备有机光电器件。
以下结合附图及若干优选实施例对本发明的技术方案作进一步的说明。
实施例1ZnO:PEI(氧化锌：聚乙烯酰亚胺)复合墨水的制备及在有机光伏器件中的应用
本实施例的具体操作工艺如下：
1.ZnO纳米颗粒的制备：取2.950g二水合醋酸锌，溶于125mL无水甲醇中，加热搅拌至60℃。取1.480g氢氧化钾，溶于65mL无水甲醇，超声溶解，将氢氧化钾的甲醇溶液逐滴快速加入醋酸锌溶液中，在60～65℃加热条件下，600rpm磁力搅拌2h。反应过程中，溶液先是由无色，然后出现白色沉淀至沉淀逐渐消失，溶液变为浅蓝色，约2h后出现白色沉淀，继续加热0.5h，停止加热，反应完成。
2.ZnO墨水制备：ZnO纳米颗粒制备完成后，反应液静置3h，移去上层清液，加入50mL无水甲醇，600rpm搅拌10min后静置过夜；上层清液和白色沉淀完全分层后移去上层清液，加入50mL无水甲醇，600rpm搅拌10min，然后4000rpm离心10min，保留沉淀即为ZnO纳米颗粒。在白色沉淀中加入10mL三氯甲烷，1mL甲醇，超声分散获得浅蓝色透明的ZnO纳米颗粒的分散液，该ZnO墨水均一分散，比较稳定。ZnO墨水在室温下保存，可以加入适量三氯甲烷-甲醇混合溶剂稀释得到不同浓度的ZnO墨水。
3.PEI墨水制备：取10mg PEI固体，加入约3.3mL无水甲醇至总质量为2.5g，超声至溶解，即得到重量浓度为0.4％的PEI墨水。
4.ZnO:PEI复合墨水的制备：取浓度为10mg/mL的ZnO墨水与重量浓度为0.4％的PEI墨水按照不同的体积比例混合来调节两者之间的重量比，超声即可得到澄清透明的ZnO:PEI复合墨水。
5.以ZnO:PEI为阴极修饰层的倒置器件的制备：倒置器件的结构包括ITO阴极，ZnO:PEI复合阴极修饰层，P3HT:PC61BM光活性层，MoO3阳极修饰层，Al阳极。通过对比不同ZnO和PEI的重量比，根据器件性能对比，得到最佳ZnO:PEI共混比例。器件结构为ITO/ZnO:PEI/P3HT:PC61BM/MoO3/Al。ZnO:PEI复合阴极修饰层采用旋涂2300rpm，1min，手套箱内124℃退火10min。根据表1器件性能参数可以看到，ZnO:PEI在重量比在25:3-25:7.5之间时，太阳能电池器件的性能变化不大，当ZnO:PEI的重量比增加至25:12和25:15时，器件短路电流和填充因子都有很大的降低，器件J-V曲线出现S-型曲线，说明ZnO:PEI的最佳重量比在25:3-25:7.5之间，增加PEI的重量时已经影响到ZnO在修饰ITO电极上的作用。
6.分别以ZnO、ZnO:PEI、PEI为阴极修饰层的倒置器件制备：分别以ZnO，ZnO:PEI，PEI为阴极修饰层，应用于倒置器件中，对比三种结构阴极修饰层对器件性能的影响。ZnO墨水，ZnO:PEI墨水，PEI墨水均采用2300rpm旋涂1min，然后在手套箱内124℃退火10min。三种结构分别作为阴极修饰层应用于结构为ITO/ETL/P3HT:PC61BM/MoO3/Al的倒置结构器件中。
根据图1的J-V曲线和表1性能参数可知，以ZnO:PEI为复合阴极修饰层的器件性能优于以单独PEI作为阴极修饰层的器件，而相比于ZnO作为阴极修饰层的器件，有利于提高器件FF，器件总体性能不会降低。从薄膜的AFM图(图3)可以看到ZnO与PEI的复合有效减少了ZnO纳米颗粒的团聚，ZnO:PEI薄膜的表面粗糙度小于ZnO薄膜的表面粗糙度。因此通过以上三种器件结构对比，可见在合适重量比的ZnO与PEI复合，不仅可以有效减少ZnO纳米颗粒的团聚，并且以复合薄膜为阴极修饰层的器件可以得到与ZnO单层作为阴极修饰层器件相当的性能。
表1 实施例1中以ZnO、ZnO:PEI、PEI作为阴极修饰层的P3HT:PC61BM体系太阳能电池的器件性能参数
器件 JSC[mA·cm-2] VOC[V] FF Mpp[％]
ZnO 0.61 7.84 0.60 2.87
ZnO:PEI(25:3,w/w) 0.60 7.64 0.61 2.80
ZnO:PEI(25:4.5,w/w) 0.60 7.57 0.63 2.86
ZnO:PEI(25:6,w/w) 0.60 7.73 0.60 2.78
ZnO:PEI(25:7.5,w/w) 0.60 7.26 0.64 2.79
ZnO:PEI(25:12,w/w) 0.60 3.91 0.17 0.40
ZnO:PFN(25:15,w/w) 0.58 0.34 0.15 0.03
PEI 0.57 5.36 0.56 1.71
实施例2：
ZnO:PEIE复合墨水的制备：取浓度为10mg/ml的ZnO墨水(其制备过程可参照实施例1)与重量浓度为0.4％的PEIE(80％甲氧基化聚乙烯亚胺)的溶液按照不同体积比混 合，超声分散得到ZnO:PEIE复合墨水。
ZnO:PEIE复合阴极修饰层制备：可通过2300rpm转速下在ITO电极表面旋涂得到ZnO:PEIE复合阴极修饰层。
实施例3：PMA:PEDOT:PSS复合墨水的制备及在有机光伏器件中的应用
1、该PMA:PEDOT:PSS复合墨水的制备工艺包括：
(1)PMA墨水的制备：取1mg三水合磷钼酸(H3PO4·12MoO3·3H2O，PMA)粉末，加入1mL重蒸异丙醇，超声至完全分散，即得到重量浓度为1mg/mL的PMA墨水。
(2)PMA:PEDOT:PSS复合墨水的制备：取浓度为1mg/mL的PMA墨水与PEDOT:PSS(Clevios PV P AI4083)墨水按照不同的体积比例混合，超声即可得到PMA:PEDOT:PSS复合墨水。
2、相应PMA:PEDOT:PSS复合薄膜的制备工艺包括：通过旋涂、刮涂等通用方法将该PMA:PEDOT:PSS复合墨水涂布在基底材料上，经干燥后形成所述复合薄膜。
如下是该PMA:PEDOT:PSS复合薄膜的表征结果。请参阅图5a，该复合薄膜在紫外光区域和近红外区域都有吸收，其中近红外光区域的吸收是由PEDOT:PSS的吸收带来的。再请参阅图5b，考察P3HT:PC61BM薄膜在沉积PMA:PEDOT:PSS前后的吸收光谱可以确认该复合薄膜可沉积在活性层表面。
3、以PMA:PEDOT:PSS复合薄膜为阳极修饰层的倒置器件的制备工艺包括：所述倒置器件的结构包括ITO阴极，ZnO阴极修饰层，PTB7:PC61BM光活性层，PMA:PEDOT:PSS阳极修饰层，Al阳极。分别以PMA、PEDOT:PSS、PMA:PEDOT:PSS、蒸镀MoO3为阳极修饰层，制备结构为ITO/ZnO/PTB7:PC61BM/阳极修饰层/Al的倒置结构器件。PMA墨水，PMA:PEDOT:PSS墨水，PEDOT墨水均采用2300rpm旋涂1min，然后在手套箱内124℃退火10min。请参阅图6a-图6c，从薄膜的AFM图可以看到纯PMA墨水在PTB7:PC61BM薄膜上形成孤岛状薄膜，其孤岛尺寸约100nm，这主要是来自PMA的团聚，因此使得PTB7:PC61BM薄膜的粗糙度由1.7nm提高至4.1nm。而PMA与PEDOT:PSS复合，使得PMA颗粒的团聚现象得到改善，从而获得PMA:PEDOT:PSS薄膜的粗糙度为2.1nm。
再请参阅图7a-图7b的J-V曲线和表2的性能参数可知，以PMA:PEDOT:PSS为复合阳极修饰层的器件性能优于以单独PMA作为阳极修饰层的器件，而相比于PMA为阳极修饰层的器件，器件的开路电压和短路电流有明显的提升，总体器件效率提高20％左右。此外，从图8a-图8d中可以看出，PMA:PEDOT:PSS复合薄膜作为阳极修饰层，得 到的器件在长时间工作中的稳定性优于单纯PEDOT:PSS、单纯PMA，以及e-MoO3的参比器件。
表2 实施例1中以PMA、PMA:PEDOT:PSS、e-MoO3作为阳极修饰层的PTB7:PC61BM体系太阳能电池的器件性能参数
Figure PCTCN2015097676-appb-000002
实施例4：PMA:PEDOT:PSS复合层在钙钛矿电池中的应用
1、该PMA:PEDOT:PSS复合墨水的制备工艺包括：
(1)PMA墨水的制备：取x mg三水合磷钼酸(H3PO4·12MoO3·3H2O，PMA)粉末，加入1mL异丙醇，超声至完全分散，即得到重量浓度为x mg/mL的PMA墨水。
(2)PMA:PEDOT:PSS复合墨水的制备：取PMA墨水与PEDOT:PSS(AI4083)墨水按10:1体积比例混合，超声即可得到一系列PMA:PEDOT:PSS复合墨水。
2、以PMA:PEDOT:PSS为阳极修饰层的钙钛矿电池的制备与性能测试：本实施例中钙钛矿电池的结构为：ITO/PMA:PEDOT:PSS/PVSK/PCBM/Al，其中单纯PEDOT:PSS修饰层也作为参比器件。表3给出器件的性能参数。可以看出以PMA:PEDOT:PSS复合物为阳极修饰层获得器件性能与含有单纯PEDOT:PSS的器件相似，说明PMA:PEDOT:PSS复合层可以作为钙钛矿电池的阳极修饰层。
表3 以10％PMA(mg/mL):PEDOT:PSS为阳极修饰层的钙钛矿电池的器件性能统计
Figure PCTCN2015097676-appb-000003
Figure PCTCN2015097676-appb-000004
实施例5：磷钨酸(H3PW12O40,PWA)：苯磺酸(PSS)复合界面层在有机太阳能电池中的应用
将1mg PWA溶于异丙醇中获得浓度为5mg/mL的墨水，将5mg苯磺酸溶于水中获得浓度为5mg/mL的溶液，取相同体积的PWA溶液和苯磺酸溶液混合，获得重量比为1：1，总重量浓度为5mg/mL的复合墨水。
基于PWA:PSS复合层的电池的制备：在ITO玻璃上，采用刮涂法制备厚度约为30nm的复合层，随后依然旋涂P3HT:PC61BM，ZnO层，最后热蒸发Al电极。图9给出该器件的J-V曲线。
实施例6：基于硅钼酸(SMA)：聚合物的复合界面层在钙钛矿太阳能电池(PVSK)中的应用
硅钼酸：复合墨水的制备：取30mg硅钼酸(SiMo12O40)溶于1mL甲醇中，同时配置溶度为3mg/mL的聚芴衍生物(CPE-K)甲醇墨水，将硅钼酸和聚芴墨水按照一定比例复合，获得总浓度为20mg/mL的复合墨水。该墨水可采用旋涂等多种方法制备获得复合界面层薄膜。
制备结构为ITO/TiO2/PVSK/SMA:CPE-K/Al的钙钛矿电池，其中复合层在电池中作为复合阳极界面层修饰Al电极，得到的器件，其性能为：VOC＝0.80V，JSC＝18.05mA/cm2，FF＝60％，PCE＝8.7％。
实施例7：磷钼酸胺(PMN)：复合界面层在有机太阳能电池中的应用
将聚乙烯吡咯烷酮(PVP)、磷钼酸胺((NH4)6PMo18O62,PMN)分别溶解于水中，获得浓度分别为10mg/mL，和浓度10mg/mL的溶液，将两种溶液以1：10的重量比混合，得到基于磷钼酸胺和聚乙烯吡咯烷酮的复合墨水(PMN：PPV)。
制备结构为ITO/PMN：PPV/PTB7:PC61BM/LiF/Al的有机太阳能电池，得到的器件性 能为：VOC＝0.73V，JSC＝13.6mA/cm2，FF＝65％，PCE＝6.5％。
实施例8：钨多酸(WA)复合界面层在有机太阳能电池中的应用
将聚乙烯吡咯烷酮(PVP)、矾多酸(H2W6O19)分别溶解于水中，获得浓度分别为2mg/mL，和浓度10mg/mL的溶液，将两种溶液以1：10的重量比混合，得到基于磷钼酸胺和聚乙烯吡咯烷酮的复合墨水(WA：PPV)。
制备结构为ITO/WA：PPV/PTB7:PC71BM/LiF/Al的有机太阳能电池，得到的器件性能为：VOC＝0.72V，JSC＝15.7mA/cm2，FF＝65％，PCE＝7.3％。
实施例9：磷钨酸(H3PW12O40,PWA)复合界面层:PEI复合物作为阴极界面层在有机太阳能电池中的应用
将1mg PWA溶于甲醇中获得浓度为5mg/mL的墨水，将1mg PEI在水中分散获得浓度为1mg/mL的溶液，取相同体积的PWA溶液和苯磺酸溶液混合，获得重量比为1：1，总重量浓度为2.5mg/mL的复合墨水。
基于PWA:PEI复合层的电池的制备：在ITO玻璃上，用旋涂法依次制备PEDOT:PSS,PffBT4T2OD:PC61BM活性层，PWA:PEI复合层，以及蒸镀Al电极。测试这一器件的性能为：VOC＝0.75V，JSC＝17.76mA/cm2，FF＝67％，PCE＝8.92％。
需要说明的是，如上实施例所采用的各种原料、工艺条件、器件材质及结构参数等均是较为典型的范例，但经过本案发明人大量试验验证，于上文所列出的其它不同类型的原料及其它工艺参数等也均是适用的，并也均可达成本发明所声称的技术效果。

Claims (26)

  1. 一种聚合物-金属化合物复合墨水，其特征在于包含：
    至少一种聚合物，
    至少一种金属化合物材料，所述金属化合物材料选自多金属氧簇化合物和纳米金属氧化物，以及，
    至少一种溶剂，用于与所述复合墨水中的其余组分配合而形成均匀流体状分散体系。
  2. 根据权利要求1所述的聚合物-金属化合物复合墨水，其特征在于：所述多金属氧簇化合物至少选自含有钼、钨、钒中的任意一种或者两种以上的组合的多金属氧簇化合物。
  3. 根据权利要求2所述的聚合物-金属化合物复合墨水，其特征在于：所述多金属氧簇化合物还含有磷、硅、锗、砷中的任意一种或者两种以上的组合。
  4. 根据权利要求2所述的聚合物-金属化合物复合墨水，其特征在于：所述多金属氧簇化合物包括Keggin型多金属氧簇化合物、Wells-Dawson型多金属氧簇化合物、Lindqvist型多金属氧簇化合物中的任意一种或者两种以上的组合。
  5. 根据权利要求2所述的聚合物-金属化合物复合墨水，其特征在于：所述多金属氧簇化合物包括金属多酸和/或金属多酸的盐。
  6. 根据权利要求2所述的聚合物-金属化合物复合墨水，其特征在于：所述聚合物包括共轭聚合物和/或非共轭聚合物。
  7. 根据权利要求2所述的聚合物-金属化合物复合墨水，其特征在于：所述聚合物包括聚苯胺、聚噻吩、聚吡咯、聚硒吩、聚磺酸、聚对甲苯磺酸、聚芴类衍生物中的任意一种或任意一种的衍生物。
  8. 根据权利要求1所述的聚合物-金属化合物复合墨水，其特征在于：所述聚合物与多金属氧簇化合物的质量比为1:0.1-1:15，尤其优选为1:1-1:3。
  9. 根据权利要求2所述的聚合物-金属化合物复合墨水，其特征在于：所述溶剂包括水、有机醇中的任意一种或两种以上的组合。
  10. 根据权利要求2所述的聚合物-金属化合物复合墨水，其特征在于所述复合材料中聚合物与多金属氧簇化合物复合物的浓度为0.5-20mg/mL，优选为3-10mg/mL。
  11. 根据权利要求1所述的聚合物-金属化合物复合墨水，其特征在于包含：
    至少一种具有脂肪胺单元的聚合物，
    至少一种纳米金属氧化物，
    用作所述溶剂的至少一种有机醇。
  12. 根据权利要求11所述的聚合物-金属化合物复合墨水，其特征在于：所述具有脂 肪胺单元的聚合物包括直链或支化的聚乙烯亚胺、端位乙氧基化或乙胺基化的聚乙烯亚胺、含聚乙烯亚胺片段的共聚物中的任一种或两种以上的组合。
  13. 根据权利要求11所述的聚合物-金属化合物复合墨水，其特征在于，所述纳米金属氧化物包含选自下列元素组的金属元素：钼、钒、钨、镍、钛、锡、锌。
  14. 根据权利要求13所述的聚合物-金属化合物复合墨水，其特征在于，所述纳米金属氧化物还包含不同于所述元素组中的任一金属元素及氧元素的金属和/或非金属元素。
  15. 根据权利要求11所述的聚合物-金属化合物复合墨水，其特征在于：所述纳米金属氧化物的粒径为3-50nm，优选为5-15nm。
  16. 根据权利要求9或11所述的聚合物-金属化合物复合墨水，其特征在于：所述有机醇包括甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、乙二醇、乙二醇单甲醚中的任一种或两种以上的组合。
  17. 根据权利要求9或11所述的聚合物-金属化合物复合墨水，其特征在于：所述溶剂还包括辅助有机溶剂，所述辅助有机溶剂包括丙酮、氯仿、甲苯、二甲苯、三甲苯、氯苯、二氯苯中的任意一种或两种以上的组合。
  18. 根据权利要求11所述的聚合物-金属化合物复合墨水，其特征在于：所述聚合物-金属化合物复合墨水中聚合物与纳米金属氧化物的重量/体积浓度为0.5-60mg/mL。
  19. 根据权利要求11所述的聚合物-金属化合物复合墨水，其特征在于：所述聚合物与纳米金属氧化物复合物的重量比为1:25-1:2.5，优选为1:6-1:4。
  20. 如权利要求1-19中任一项所述聚合物-金属化合物复合墨水的制备方法，其特征在于包括：将所述聚合物与所述金属化合物材料于溶剂中均匀混合而形成所述复合材料。
  21. 如权利要求20所述的制备方法，其特征在于包括：将所述聚合物溶于和/或分散于溶剂中形成第一体系，以及将所述金属化合物材料分散于溶剂中形成第二体系，再将该第一体系和第二体系均匀混合，从而形成所述复合材料。
  22. 一种薄膜，其特征在于它主要由权利要求1-19中任一项所述的聚合物-金属化合物复合墨水形成。
  23. 一种薄膜的制备方法，其特征在于包括：通过涂布或印刷方式将权利要求1-19中任一项所述的聚合物-金属化合物复合墨水施加到基底上而形成所述薄膜。
  24. 根据权利要求23所述的制备方法，其特征在于：所述涂布或印刷方式包括旋转涂膜、刮刀涂布、狭缝涂布、喷墨印刷、丝网印刷、凹版印刷、柔版印刷、柔版转印方法中的任意一种或两种以上的组合。
  25. 一种装置，其特征在于包含权利要求22所述的薄膜。
  26. 如权利要求25所述的装置，其特征在于：所述装置为具有电-光和/或光-电转换特性的光电器件；所述装置包括太阳能电池器件或电致发光二极管器件。
PCT/CN2015/097676 2014-12-17 2015-12-17 聚合物-金属化合物复合墨水及其制备方法与应用 WO2016095828A1 (zh)

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