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WO2015169243A1 - 金属氧化物-导电聚合物-醇组合物、其制备方法及应用 - Google Patents

金属氧化物-导电聚合物-醇组合物、其制备方法及应用 Download PDF

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WO2015169243A1
WO2015169243A1 PCT/CN2015/078482 CN2015078482W WO2015169243A1 WO 2015169243 A1 WO2015169243 A1 WO 2015169243A1 CN 2015078482 W CN2015078482 W CN 2015078482W WO 2015169243 A1 WO2015169243 A1 WO 2015169243A1
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metal oxide
conductive polymer
solvent
alcohol composition
oxide
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PCT/CN2015/078482
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English (en)
French (fr)
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骆群
马昌期
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深圳市博世知识产权运营有限公司
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Publication of WO2015169243A1 publication Critical patent/WO2015169243A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • 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
    • C09D11/52—Electrically conductive inks
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

Definitions

  • the invention particularly relates to a metal oxide-conductive polymer-alcohol composition, a preparation method and application thereof, and belongs to the technical field of photo-electric or electro-optical conversion materials.
  • Organic optoelectronic devices Compared with inorganic optoelectronic devices, organic optoelectronic devices have the advantages of low material cost, simple manufacturing process, softness, and large-area manufacturing.
  • Organic optoelectronic devices have a multilayer film structure including: an anode, a hole buffer layer, an organic photoactive layer, an electron buffer layer, and a cathode. Due to the difference in work function between the anode/anode electrode and the organic active layer, the contact between the electrode and the organic substance is a non-ohmic contact, thereby bringing an interface barrier.
  • the buffer layer material is between the electrode and the organic active layer, and functions to adjust the work function of the electrode.
  • the anode material commonly used in the inverted structure organic photovoltaic device is ITO glass, and the work function is ⁇ 4.8 eV.
  • the most common method of work function is to deposit a layer of PEDOT:PSS with a work function of 5.1 eV on the surface of ITO, so that the work function of the anode and the HOMO level of poly(3-hexylthiophene) (P3HT) of the organic layer material (- 5.1 eV) conforms to achieve high hole transport efficiency.
  • buffer layer materials include metal oxides, polymers and organic small molecule materials.
  • Metal oxide materials have high stability, but many deposition methods are required to achieve film deposition.
  • the polymer material has the advantages of good solution film forming property, and is suitable for large-scale printing technology, but the material has poor water and oxygen resistance, and the mature polymer buffer material system is also very limited.
  • Small molecular materials also have the disadvantage of requiring vacuum deposition while having poor stability.
  • researchers have gradually carried out research and development work on metal oxide nanoparticle inks; although organic photoelectric devices have obtained some results with high stability and excellent device performance, The agglomeration of nanoparticles in the ink is unavoidable. The agglomerated nanoparticles will introduce island points that cause device short-circuit or performance degradation during deposition into a thin film.
  • organic photovoltaic devices can be divided into two types: traditional structures and inverted structures.
  • the organic solar cell with inverted structure is ITO cathode, electron buffer layer, organic active layer, hole buffer layer and metal anode in order of light incident direction.
  • MoO x or PEDOT:PSS is a commonly used hole buffer layer.
  • MoO x has a work function of 5.3 eV, which can modify Ag (4.3eV) and Al (4.2eV) electrodes commonly used in organic optoelectronic devices for devices such as OLEDs and OPVs.
  • PEDOT PSS consists of PEDOT and PSS, which are 3,4-ethylenedioxythiophene polymer and polystyrene sulfonate. The former is a conductive conjugated polymer and the latter is a polymer acidic substance.
  • PEDOT The work function of PSS is 5.2 eV.
  • the organic solar cell of the upright structure has an ITO anode, a hole buffer layer, an organic photoactive layer, an electron buffer layer, and a metal electrode according to the light incident direction. It is necessary to deposit LiF or ZnO (TiO x ) as an electron buffer layer on the organic photoactive layer to improve the electron collection efficiency of the metal electrode.
  • the ZnO(TiO x ) prepared by the solution method has been reported to be applied to the organic solar cell with an upright structure.
  • the process requirements for preparing the electronic buffer layer by this method are required. Higher, also leads to poor repeatability of the device.
  • One of the objects of the present invention is to provide a metal oxide-conductive polymer-alcohol composition
  • a metal oxide-conductive polymer-alcohol composition comprising:
  • At least one semiconducting metal oxide is uniformly dispersed in the composition mainly in the form of nanoparticles
  • At least one electrically conductive polymer comprising at least one conjugated polymer
  • a solvent comprising at least one organic alcohol to render the composition fluid and to enhance the wettability of the composition on the surface of the organic film.
  • the semiconducting metal oxide may be selected from, but not limited to, an oxide of molybdenum, an oxide of vanadium, an oxide of tungsten, an oxide of nickel, an oxide of zinc, an oxide of titanium, or Combination of two or more.
  • the conductive polymer includes a composite formed of a conjugated polymer and at least one acidic co-solvent.
  • the conjugated polymer includes any one or a combination of two or more of polyaniline, polypyrrole, polythiophene, polyselenophene, polyfluorene, polyparaphenylenevinylene, and derivatives thereof.
  • the acidic co-solvent includes acetic acid, propionic acid, butyric acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid, or a non-fluorinated acidic polymer.
  • the non-fluorinated acidic material includes an acidic polymer including poly-p-styrenesulfonic acid or poly(2-acrylamido-2-methyl-1-propanesulfonic acid).
  • a second object of the present invention is to provide a method for preparing the aforementioned metal oxide-conductive polymer-alcohol composition, comprising: at least taking semiconductor nano metal oxide particles, at least one organic alcohol, and at least one conductive polymer The mixture is uniformly mixed to form the metal oxide-conductive polymer-alcohol composition in a fluid state.
  • a third object of the present invention is to provide a film comprising any of the foregoing metal oxide-conductive polymer-alcohol compositions.
  • a fourth object of the present invention is to provide a method of preparing the foregoing film, comprising: printing a film by using any of the foregoing metal oxide-conductive polymer-alcohol compositions.
  • a fifth object of the present invention is to provide an organic electronic device comprising any of the foregoing films.
  • the organic electronic device has electro-optical and/or photo-electric conversion characteristics.
  • the metal oxide-conductive polymer-alcohol combination The material is easy to prepare, low in cost, and can be used as a buffer layer material with high stability and good film forming property, and can be processed into a buffer layer film by spin coating or inkjet printing, for example, a hole buffer layer and The electron buffer layer and the formed hole buffer layer have a high work function, satisfy the requirement of improving the work function of the metal anode, have good wettability to the organic active layer, and can form on the surface of the organic active layer without external additives or surface treatment.
  • the dense and low surface roughness of the film can effectively reduce the work function of the metal electrode, and the film formation property on the organic photoactive layer is high, which can greatly reduce the preparation difficulty of the photovoltaic device and improve the device. Repeatability.
  • Example 1c is an XPS diagram of the MoO x film obtained in Example 1;
  • 3a-3b are AFM diagrams of deposited MoO x and MoO x -PEDOT:PSS films on P3HT:PC 61 BM in Example 1;
  • Example 5 is a JV curve of an inverted device in which MoO x -PEDOT:PSS is a hole buffer layer in Example 2.
  • one aspect of the present invention provides a metal oxide-conductive polymer-alcohol composition comprising:
  • At least one semiconducting metal oxide is uniformly dispersed in the composition mainly in the form of nanoparticles
  • At least one electrically conductive polymer comprising at least one conjugated polymer
  • a solvent comprising at least one organic alcohol to render the composition fluid and enhance The composition is wettable on the surface of the organic film.
  • the size of the nanoparticles is 2 to 20 nm, and the morphology is a point, a rod, a column, a line, etc., and is not limited thereto.
  • the weight ratio of the semiconductor metal oxide and the conductive polymer is 0.01-0.99:1;
  • the weight ratio of the metal oxide to the polymer in the composition is 20 to 80%
  • the semiconducting metal oxide may be selected from, but not limited to, an oxide of molybdenum, an oxide of vanadium, an oxide of tungsten, an oxide of nickel, an oxide of zinc, an oxide of titanium, or A combination of two or more kinds, such as molybdenum oxide, tungsten oxide, titanium oxide, zinc oxide, nickel oxide, or the like.
  • the conjugated polymer may be selected from, but not limited to, any one or two or more of polyaniline, polypyrrole, polythiophene, polyselenophene, polyfluorene, polyetherimide or a derivative thereof. combination.
  • the acidic substance may be selected from a non-fluorinated polymer such as poly-p-styrenesulfonic acid or poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and is not limited thereto.
  • Another aspect of the present invention provides a method for producing the aforementioned metal oxide-conductive polymer-alcohol composition, which can be obtained by uniformly mixing semiconductor nano metal oxide particles, conductive polymer ink or semiconductor nano metal oxide particles. It is added to a conductive polymer ink simultaneously with a solvent such as an alcohol, and is obtained by ultrasonic dispersion.
  • the preparation method comprises: at least taking nano metal oxide particles and or ink, at least one organic alcohol, and at least one conductive polymer ink uniformly mixed to form the metal oxide in a fluid state - Conductive polymer-alcohol composition.
  • the preparation method may include:
  • the metal element contained in the metal and/or metal oxide powder may be selected from, but not limited to, molybdenum, vanadium, tungsten. Any one or a combination of two or more of nickel, zinc, and titanium;
  • the nano metal oxide-containing ink obtained in the step (2) is uniformly mixed with the conductive polymer ink to form the metal oxide-conductive polymer-alcohol composition.
  • the semiconductor nano metal oxide particles obtained in the step (1) and a solvent such as an alcohol or acetone may be directly added to the conductive polymer ink at a suitable mass concentration to obtain the metal oxide-conductive polymer-alcohol. combination.
  • the first solvent and the second solvent may be selected from, but not limited to, any one or a combination of two or more of water, ethanol, propanol and isopropanol.
  • preparation method may further include:
  • the third solvent is added to the supernatant, and then ultrasonically dispersed to form a semiconductor nano metal oxide ink, and then a conductive polymer dispersion mainly composed of a conductive polymer and a fourth solvent, and at room temperature.
  • the metal oxide-conductive polymer-alcohol composition is formed by uniformly mixing by ultrasonic dispersion or magnetic stirring.
  • the third solvent and the fourth solvent may be selected from, but not limited to, any one or a combination of two or more of water, ethanol, propanol and isopropanol, but the third solvent and the fourth solvent cannot simultaneously For water.
  • the concentration of the semiconductor nano metal oxide ink is preferably 5 to 30 mg/ml.
  • Still another aspect of the present invention provides the use of the foregoing metal oxide-conductive polymer-alcohol composition in the preparation of an organic electronic device, particularly an organic photovoltaic device, for example, as a buffer layer material for an organic photovoltaic device.
  • a buffer layer film is prepared by spin coating, ink jet printing or the like using the aforementioned metal oxide-conductive polymer-alcohol composition as an ink.
  • a film comprising any one of the foregoing metal oxides - Conductive polymer-alcohol composition.
  • the method for preparing the foregoing film may include: printing any one of the foregoing metal oxide-conductive polymer-alcohol compositions into a film, wherein the printing method may be selected from, but not limited to, spin coating, inkjet, wire mesh or Gravure printing.
  • the printing method may be selected from, but not limited to, spin coating, inkjet, wire mesh or Gravure printing.
  • film formation can also be carried out by other known solution processing methods such as doctor blade coating.
  • Still another aspect of the present invention provides an organic electronic device comprising any one of the foregoing metal oxide-conductive polymer-alcohol compositions or any of the foregoing films.
  • the organic electronic device can be a solar cell or an OLED device.
  • the organic electronic device may be an inverted-structure solar cell or a bottom-emitting OLED device including an anode/hole buffer layer/active layer (light-emitting layer)/electron buffer layer/cathode distributed in the order of illumination.
  • the organic electronic device may be a positive-structure solar cell or a top-emitting OLED device including a cathode/electron buffer layer/active layer (light-emitting layer)/hole buffer layer/anode sequentially distributed in the direction of illumination.
  • the electron buffer layer may comprise the aforementioned film.
  • the electronic device may be a single-layer structure device mainly formed by the foregoing anode, hole buffer layer, active layer, electron buffer layer, cathode, or the like, or may be constructed based on the above single-layer structure device.
  • Layer structure device mainly formed by the foregoing anode, hole buffer layer, active layer, electron buffer layer, cathode, or the like, or may be constructed based on the above single-layer structure device.
  • the organic electronic device has electro-optical and photoelectric conversion characteristics, and may be, for example, an organic light-emitting device, a photovoltaic cell, or the like.
  • a metal oxide-conductive polymer-alcohol composition is prepared as follows:
  • molybdenum powder, vanadium powder, tungsten powder, nickel powder, zinc powder and other metals or oxide powders as raw materials, adding hydrogen peroxide in water, ethanol or isopropanol, and oxidizing reaction under continuous stirring 12-24 In an hour, a mixture containing metal oxide nanoparticles was obtained.
  • the synthesis of molybdenum oxide nanoparticles is obtained by reacting molybdenum powder as a raw material in an ethanol solvent by adding hydrogen peroxide for 24 hours.
  • the mixture obtained by the reaction is subjected to vacuum drying-ultrasonic dispersion-centrifugation-ultrasonic dispersion multi-step treatment to finally obtain an alcohol or water-dispersed metal oxide ink.
  • an ink obtained by dissolving MoO x (2 ⁇ x ⁇ 3) ethanol is prepared: first, the mixture obtained by the reaction is allowed to stand for about 2 hours. There is a black precipitate at the bottom of the reaction vessel, which is an unreacted metal molybdenum powder. Afterwards, the upper blue supernatant was removed by a pipetting chamber, vacuumed in a vacuum oven for 2 hours, and then dried under vacuum overnight. The dried powder was redispersed in ethanol, and a stably dispersed nano-MoO x ink was obtained via ultrasonic dispersion-high speed centrifugation-ultrasonic dispersion.
  • a preferred reaction system is: weighing 200 mesh of high-purity molybdenum powder as a reaction raw material, adding anhydrous ethanol, Magnetic stirring for 30 minutes allowed the molybdenum powder to be uniformly dispersed in ethanol. The concentration was 40% hydrogen peroxide, slowly added to the molybdenum powder-alcohol dispersion system, and magnetic stirring was continued for about 24 hours. The reaction product was allowed to stand for precipitation, the bottom precipitate was removed, and the supernatant was retained. The supernatant liquid was placed in a vacuum drying oven to remove the solvent by vacuum drying at room temperature to obtain a nano-oxide powder.
  • the oxide nanopowder obtained by drying was again dispersed in ethanol, isopropanol or water, and dispersed by ultrasonication for a long time, followed by centrifugation at 4000 rpm for 10 minutes. After centrifugation, the bottom precipitate is removed and the supernatant is left to obtain a nano-oxide ink.
  • the nano-oxide ink concentration can be calibrated by taking a certain volume of ink and vacuum-drying into a powder, weighing the mass of the powder, and calculating the ratio of mass to volume. Wherein, the concentration of the nano-oxide ink is preferably 8 to 10 mg/ml.
  • the aforementioned nano-oxide ink can be formulated into different concentrations of ink by adding a solvent such as alcohol or water.
  • a metal oxide-conductive polymer-alcohol composition is obtained by mixing an alcohol-dispersed phase of a metal oxide (for example, the aforementioned nano-oxide ink) with a conductive polymer in a volume ratio.
  • a metal oxide for example, the aforementioned nano-oxide ink
  • a conductive polymer for example, the aforementioned nano-oxide ink
  • a metal oxide-conductive polymer-alcohol composition is obtained by mixing an alcohol-dispersed phase of a metal oxide (for example, the aforementioned nano-oxide ink) with a conductive polymer in a volume ratio.
  • the foregoing metal oxide-conductive polymer-alcohol composition when applied to form a film, such as a buffer layer, it can be prepared by coating a doctor blade, inkjet printing or the like on an organic surface or an ITO electrode to obtain an anode buffer.
  • the composite hole buffer layer of the inverted structure organic photovoltaic device can be obtained by spin coating on the surface of the organic active layer.
  • the buffer layer preparation process by the metal oxide-conductive polymer-alcohol composition prepared by the process of the present invention is more compatible with the printing method, and the film quality is high. And the obtained hole buffer layer is low in sensitivity to the atmosphere.
  • the invention has higher stability, and when it is deposited on the surface of the organic active layer, the ultraviolet ozone, oxygen plasma, etc. of the surface of the organic photoactive layer can be avoided.
  • the disadvantage of the surface treatment, or the introduction of a surfactant when modifying the polymer results in a decrease in the performance of the polymer buffer layer.
  • the metal oxide particles have a size of about 5 nm in the MoO x ink, and the size is uniform and the monodispersity is good.
  • Mo3d contains two Gaussian peaks of 232.6eV and 231.6eV, both of which correspond to Mo 6+ , indicating that the valence state of Mo in MoO x is mainly +6 valence;
  • the figure shows that the peak position of O1s is 530.5 eV, which corresponds to O 2- .
  • inverted device with MoO x -PEDOT:PSS as hole buffer layer Inverted device structure including ITO cathode, ZnO cathode buffer layer, P3HT: PC 61 BM active layer, MoO x -PEDOT:PSS composite hole buffer Layer and Al or Ag anode.
  • the structure of the device and the reference device are:
  • ITO/ZnO/P3HT PC 61 BM/MoO x /Ag
  • ITO/ZnO/P3HT PC 61 BM/MoO x -PEDOT:PSS/Ag,
  • ITO/ZnO/P3HT PC 61 BM/e-MoO 3 /Ag.
  • a MoO x hole buffer layer (s-MoO x ) was spin-coated on a P3HT:PC 61 BM film and spin-coated at 3500 rpm for 60 s to obtain a film having a thickness of about 100 nm.
  • Spin-coated MoO x -PEDOT:PSS was spin-coated at 2000-5000 rpm for 60 s, at 2200 rpm, 3500 rpm, 5000 rpm to obtain films with thicknesses of 75 nm, 50 nm and 30 nm, respectively.
  • the s-MoO x , MoO x -PEDOT:PSS film is spin-coated on the P3HT:PC 61 BM film, and its absorption in the ultraviolet and near-infrared regions is enhanced, just like s-MoO x and PEDOT.
  • the absorption spectrum of PSS is consistent, indicating that s-MoO x , MoO x -PEDOT:PSS ink can be deposited on the surface of P3HT:PC 61 BM by solution spin coating.
  • the surface roughness of the s-MoO x and MoO x -PEDOT:PSS composite films on the AFM image of the film is 2.8 nm and 0.8 nm, respectively, and can be seen by compounding with PEDOT:PSS, s Particle agglomeration on the -MoO x film is clearly improved.
  • FIG. 4 and Table 1 below it can be seen that different thicknesses of MoO x -PEDOT:PSS are inverted devices of the hole buffer layer (shown as MoO x -PEDOT:PSS in the following table), and the MoO x layer is spin-coated as a cavity.
  • the device of the buffer layer (shown as s-MoO 3 in the following table) and the device for vacuum-evaporating MoO 3 as a hole buffer layer (shown as e-MoO 3 in the following table) have comparable performance.
  • MoO x -PEDOT PSS is the performance parameter of the device for inverting the hole buffer layer and the device for vacuum evaporation of MoO 3 as the hole buffer layer.
  • the device structure (in the order of sequential lamination, the same below) is: ITO/ZnO/ P3HT: PC 61 BM/MoO x -PEDOT: PSS/Ag.
  • ITO/ZnO/P3HT PC 61 BM/MoO x (2 ⁇ x ⁇ 3)-PEDOT:PSS/Al,
  • ITO/ZnO/P3HT PC 61 BM/e-MoO 3 /Al.
  • the MoO x -PEDOT:PSS film prepared by the solution method can also improve the work function of Al, and obtain the device performance equivalent to that of the reference device ITO/ZnO/P3HT:PC 61 BM/e-MoO 3 /Al.
  • the mixture was allowed to stand for 2 hours, and the supernatant liquid was placed in a vacuum drying oven to remove the solvent by vacuum drying at room temperature to obtain a nano-oxide powder.
  • the solid powder obtained by drying was again ultrasonically dispersed by adding an appropriate amount of ethanol for 10 minutes, and then centrifuged at 4000 rpm for 10 minutes. After centrifugation, the supernatant was taken and dispersed by ultrasonication to obtain a nano-ZnO ink having a particle size of 5 to 20 nm.
  • the obtained nano ZnO ink was diluted with an appropriate amount of ethanol to be diluted to a different concentration of 10 mg/ml of ink for use.
  • the ZnO-PFN-methanol electronic buffer layer can be obtained by spin coating the above ZnO-PFN-methanol ink on a P3HT:PC 61 BM film at 2000 rpm.
  • the electronic buffer layer has properties similar to those of Embodiment 1-2.

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Abstract

公开了一种金属氧化物-导电聚合物-醇组合物、其制备方法及应用。该组合物包含：至少一种半导体金属氧化物，主要以纳米颗粒的形态均匀分散于所述组合物中；至少一种导电聚合物，所述导电聚合物包含至少一种共轭高分子；以及，包含至少一种有机醇的溶剂，用以使所述组合物呈流体状，并提高该组合物在有机薄膜表面的浸润性；在该制备方法中，半导体纳米金属氧化物颗粒可由金属或者其氧化物粉末通过与双氧水直接制备而得，且所述组合物的表面能可以通过金属氧化物与导电聚合物之间的比例进行调节。由所述组合物沉积制得的薄膜可以作为有机电子器件中的缓冲层，实现金属电极与有机活性层之间的欧姆接触。

Description

金属氧化物-导电聚合物-醇组合物、其制备方法及应用 技术领域
本发明特别涉及一种金属氧化物-导电聚合物-醇组合物，其制备方法及应用，属于光-电或电-光转换材料技术领域。
背景技术
相比于无机光电器件，有机光电器件具有材料成本低，制造工艺简单，轻柔，可大面积制造等优点。有机光电器件都有多层膜结构组成，包括：阳极,空穴缓冲层，有机光活性层，电子缓冲层和阴极等。由于阴/阳电极与有机活性层间存在功函数差异，导致电极与有机物间的接触为非欧姆接触，从而带来界面势垒。缓冲层材料处于电极和有机活性层之间，起到调节电极功函数的作用，例如在倒置结构的有机光伏器件中常用的阳极材料为ITO玻璃，其功函数为～4.8eV.为了提高ITO的功函数，最常用的方法是在ITO表面沉积一层功函数为5.1eV的PEDOT:PSS层，使得阳极的功函数与有机层材料聚(3-己基噻吩)(P3HT)的HOMO能级(-5.1eV)符合，获得高的空穴传输效率。
目前常用的缓冲层材料包括金属氧化物，聚合物和有机小分子材料。金属氧化物材料稳定性高，但是多需要真空沉积方法实现薄膜的沉积。聚合物材料具有溶液化成膜性好的优点，适合大规模印刷技术，但是材料的耐水、氧稳定性较差，目前成熟的聚合物缓冲材料体系亦十分有限。小分子材料也存在需要真空沉积的缺点，同时稳定性差的缺点。为了获得高稳定性的全溶液加工器件，研究人员逐步开展了金属氧化物纳米颗粒墨水的研究和开发工作；虽然用于有机光电器件获得了一些兼具稳定性高，器件性能优异的结果，但是纳米颗粒在墨水中的团聚不可避免。团聚的纳米颗粒在沉积成薄膜的过程中，将引入造成器件短路或者性能下降的孤岛点。
更为具体的讲，以有机光伏为例：有机光伏器件(OPV)的构成可以分为传统结构和倒置结构两种。其中倒置结构的有机太阳能电池按照光入射方向依次为ITO阴极，电子缓冲层，有机活性层，空穴缓冲层，金属阳极。其中MoOx 或PEDOT:PSS作为常用的空穴缓冲层。MoOx的功函数为5.3eV，可以修饰有机光电器件常用的Ag(4.3eV)和Al(4.2eV)电极，用于OLED以及OPV等器件中。PEDOT:PSS由PEDOT和PSS两种物质组成，分别为3，4-乙撑二氧噻吩聚合物和聚苯乙烯磺酸盐，前者为导电共轭高分子，后者为高分子酸性物质。PEDOT:PSS的功函数为5.2eV，作为有机光电器件的空穴缓冲层材料其溶液法沉积薄膜技术已经非常成熟。因为倒置结构的有机太阳能电池以高功函数的金属作为阳极，所以不易被空气氧化，具有更长的寿命。高功函数的金属电极也适合在空气中加工，所以通常认为倒置结构有机太阳能电池与印刷加工工艺兼容。尽管如此，但是由于有机活性层疏水性强，而MoOx和PEDOT:PSS都为水溶性材料，所以使用溶液法加工在有机活性层上沉积阳极缓冲层尚比较困难。目前，沉积MoOx多采用真空蒸镀方法实现，设备要求高，与印刷法制备大面积有机光伏工艺兼容性差。在有机薄膜层上沉积PEDOT:PSS则需要在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。表面活性剂的后期去除比较困难。以Plasma或者UV O3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。
再例如正置结构的有机太阳能电池，按照光入射方向，其结构分别为ITO阳极，空穴缓冲层，有机光活性层，电子缓冲层，和金属电极。需要在有机光活性层上沉积LiF或者ZnO(TiOx)作为电子缓冲层，提高金属电极的电子收集效率。溶液方法制备的ZnO(TiOx)应用于正置结构的有机太阳能电池虽然已有报道，但是由于纳米颗粒容易团聚，成膜性较差的问题，采用这种方法制备电子缓冲层对于工艺的要求较高，也导致器件的重复性较差。
发明内容
针对现有技术的不足，本发明的目的之一在于提供一种金属氧化物-导电聚合物-醇组合物，其包括：
至少一种半导体金属氧化物，主要以纳米颗粒的形态均匀分散于所述组合物中；
至少一种导电聚合物，所述导电聚合物包含至少一种共轭高分子；
以及，包含至少一种有机醇的溶剂，用以使所述组合物呈流体状以及提高所述组合物在有机薄膜表面的浸润性。
进一步的，所述半导体金属氧化物可选自但不限于钼的氧化物、钒的氧化物、钨的氧化物、镍的氧化物、锌的氧化物、钛的氧化物中的任意一种或两种以上的组合。
所述的导电聚合物包括由共轭高分子与至少一种酸性助溶剂形成的复合物。
所述的共轭高分子包括聚苯胺、聚吡咯、聚噻吩、聚硒吩、聚芴，聚对苯撑乙烯及它们的衍生物中的任意一种或两种以上的组合。
所述的酸性助溶剂包括乙酸、丙酸、丁酸、苯甲酸、苯磺酸、对甲苯磺酸、或非氟化的酸性聚合物。
所述非氟化的酸性物质包括酸性聚合物包括聚对苯乙烯磺酸或聚(2-丙烯酰氨基-2-甲基-1-丙烷磺酸)。
本发明的目的之二在于提供一种制备前述金属氧化物-导电聚合物-醇组合物的方法，其包括：至少取半导体纳米金属氧化物颗粒、至少一种有机醇以及至少一种导电聚合物均匀混合，形成呈流体状的所述金属氧化物-导电聚合物-醇组合物。
本发明的目的之三在于提供一种薄膜，其包含前述的任一种金属氧化物-导电聚合物-醇组合物。
本发明的目的之四在于提供一种制备前述薄膜的方法，包括：取前述的任一种金属氧化物-导电聚合物-醇组合物印刷成膜。
本发明的目的之五在于提供一种有机电子器件，其包含前述的任一种薄膜。
进一步的，所述有机电子器件具有电-光和/或光-电转换特性。
与现有技术相比，本发明的优点包括：该金属氧化物-导电聚合物-醇组合 物易于制备，成本低廉，可以作为具有稳定性高、成膜性好等特点的缓冲层材料，并可以通过旋涂或者喷墨印刷等多种方式加工形成缓冲层薄膜，例如空穴缓冲层和电子缓冲层，而且所形成的空穴缓冲层功函数高，满足提高金属阳极功函数的要求，对有机活性层浸润性好，不需要外加添加剂或者进行表面处理，便可以在有机活性层表面形成致密、表面粗糙度低的薄膜，所形成的电子缓冲层可以有效降低金属电极的功函数，在有机光活性层上的成膜性高，进而可大幅降低光电器件的制备难度，提高器件的可重复性。
附图说明
图1a-1b分别是实施例1中合成的MoOx纳米颗粒的TEM和HRTEM图；
图1c是实施例1所获MoOx薄膜的XPS图；
图2a-2b分别是实施例1中P3HT:PC61BM薄膜上旋涂MoOx-PEDOT:PSS层前后的吸收光谱图；
图3a-3b是实施例1中P3HT:PC61BM上沉积MoOx和MoOx-PEDOT:PSS薄膜的AFM图；
图4是实施例1中以不同厚度MoOx-PEDOT:PSS为空穴缓冲层的太阳能电池的J-V曲线；
图5是实施例2中以MoOx-PEDOT:PSS为空穴缓冲层的倒置器件的J-V曲线。
具体实施方式
如前所述，鉴于现有技术中的不足，本发明的一个方面提供了一种金属氧化物-导电聚合物-醇组合物，其包括：
至少一种半导体金属氧化物，主要以纳米颗粒的形态均匀分散于所述组合物中；
至少一种导电聚合物，所述导电聚合物包含至少一种共轭高分子；
以及，包含至少一种有机醇的溶剂，用以使所述组合物呈流体状以及提高 所述组合物在有机薄膜表面的浸润性。
进一步的，所述纳米颗粒尺寸为2～20nm，形貌为点，棒，柱，线等，且不限于此。
进一步的，在所述的金属氧化物-导电聚合物-醇组合物中，所述半导体金属氧化物和导电聚合物的重量含量比为0.01-0.99:1；
优选的，在所述组合物中所述金属氧化物与聚合物的重量含量比为20～80％
进一步的，所述半导体金属氧化物可选自但不限于钼的氧化物、钒的氧化物、钨的氧化物、镍的氧化物、锌的氧化物、钛的氧化物中的任意一种或两种以上的组合，例如氧化钼、氧化钨、氧化钛、氧化锌、氧化镍等。
进一步的，所述共轭高分子可选自但不限于聚苯胺、聚吡咯、聚噻吩、聚硒吩、聚芴、聚醚酰亚胺或其衍生物中的任意一种或两种以上的组合。
进一步的，所述酸性物质可选自非氟化的聚合物，例如聚对苯乙烯磺酸或聚(2-丙烯酰氨基-2-甲基-1-丙烷磺酸)，且不限于此。
本发明的另一个方面提供了前述金属氧化物-导电聚合物-醇组合物的制备方法，其可以通过将半导体纳米金属氧化物颗粒、导电聚合物墨水均匀混合获得或者将半导体纳米金属氧化物颗粒与醇等溶剂同时加入至导电聚合物墨水中，经超声分散获得。
在一可行实施方案中，该制备方法包括：至少取纳米金属氧化物颗粒和或墨水、至少一种有机醇以及至少一种导电聚合物墨水均匀混合，形成呈流体状的所述金属氧化物-导电聚合物-醇组合物。
进一步的，前述金属氧化物-导电聚合物-醇组合物材料
作为可选的实施方案之一，该制备方法可以包括：
(1)取金属和/或金属氧化物粉体与双氧水在第一溶剂中混合进行氧化反应，而后将反应混合物静置，弃去沉淀物，并采用业界习用的方式，例如真空 干燥方法除去所获上清液中的溶剂，获得含纳米金属氧化物的粉体，所述金属和/或金属氧化物粉体中所含的金属元素可选自但不限于钼、钒、钨、镍、锌、钛中的任意一种或两种以上的组合；
(2)将步骤(1)所获粉体均匀分散于第二溶剂中，并进行离心处理，而后取上清液超声分散，形成含纳米金属氧化物的墨水；
(3)将步骤(2)所获含纳米金属氧化物的墨水与导电聚合物墨水均匀混合，形成所述金属氧化物-导电聚合物-醇组合物。
或者，也可按合适的质量浓度取步骤(1)获得的半导体纳米金属氧化物颗粒以及醇、丙酮等溶剂直接加入至导电聚合物墨水中，从而获得所述金属氧化物-导电聚合物-醇组合物。
其中，所述第一溶剂和第二溶剂可选自但不限于水、乙醇、丙醇和异丙醇中的任一种或两种以上的组合。
进一步的，所述制备方法还可包括：
在步骤(2)中，经上清液加入第三溶剂，再超声分散，形成半导体纳米金属氧化物墨水，再与主要由导电聚合物和第四溶剂组成的导电聚合物分散液，并在室温下通过超声分散或者磁力搅拌均匀混合，形成所述金属氧化物-导电聚合物-醇组合物。其中，所述第三溶剂和第四溶剂可选自但不限于水、乙醇、丙醇和异丙醇中的任一种或两种以上的组合，但所述第三溶剂和第四溶剂不能同时为水。
其中，所述半导体纳米金属氧化物墨水的浓度优选为5～30mg/ml。
本发明的又一个方面提供了前述金属氧化物-导电聚合物-醇组合物在制备有机电子器件，特别是有机光电器件中的应用，例如，作为有机光电器件的缓冲层材料。
例如，以前述金属氧化物-导电聚合物-醇组合物为墨水，通过旋涂，喷墨打印等方法制备得到缓冲层薄膜。
本发明的再一个方面提供了一种薄膜，其包含前述的任一种金属氧化物- 导电聚合物-醇组合物。
进一步的，前述薄膜的制备方法可包括：取前述的任一种金属氧化物-导电聚合物-醇组合物印刷成膜，其中印刷方式可以选自但不限于旋涂、喷墨、丝网或凹版印刷。当然也可采用刮刀涂布等其它业界悉知的溶液加工方式制备成膜。
本发明的再一个方面提供了一种有机电子器件，其包含前述的任一种金属氧化物-导电聚合物-醇组合物或前述的任一种薄膜。
在一典型实施案例中，所述有机电子器件可以为太阳能电池或OLED器件。
例如，所述有机电子器件可以为包含沿光照方向依次分布的阳极/空穴缓冲层/活性层(发光层)/电子缓冲层/阴极的倒置结构太阳能电池或底发射OLED器件。又例如，所述有机电子器件可以为包含沿光照方向依次分布的阴极/电子缓冲层/活性层(发光层)/空穴缓冲层/阳极的正置结构太阳能电池或顶发射OLED器件。其中，所述电子缓冲层可包含前述薄膜。
进一步的，所述电子器件可以为主要由前述阳极、空穴缓冲层、活性层、电子缓冲层和阴极等形成的单层结构器件，或者也可以为以上述单层结构器件为基础构建的多层结构器件。
进一步的，所述有机电子器件具有电光及光电转换特性，例如，可以为有机发光器件，光伏电池等。
在一更为具体的实施例中，一种金属氧化物-导电聚合物-醇组合物的制备方法如下：
(1)以钼粉、钒粉、钨粉、镍粉、锌粉等金属或者其氧化物粉末为原料，在水、乙醇或异丙醇中，加入双氧水，在持续搅拌下氧化反应12～24小时，获得含有金属氧化物纳米颗粒的混合物。例如，在一些实施例中，氧化钼纳米颗粒的合成是通过以钼粉为原料，在乙醇溶剂中，加入双氧水反应24小时获得的。
(2)反应所得混合物先后经过真空干燥-超声分散-离心-超声分散多步处理，最后得到醇或者水分散的金属氧化物墨水。以制备MoOx(2<x<3)乙醇分散的墨水为例：首先将反应所得的混合物静置约2小时。反应容器底部有黑色沉淀物，为未反应完全的金属钼粉末。后用移液腔移取上层蓝色清液，置于真空干燥箱中抽真空2小时，后保持在真空条件下干燥过夜。将干燥所得粉末再次分散于乙醇中，经由超声分散-高速离心-超声分散获得稳定分散的纳米MoOx墨水。
更进一步的，以MoOx(2<x<3)-PEDOT:PSS-乙醇组合物为例，优选的反应体系为：称取200目大小的高纯钼粉末为反应原料，加入无水乙醇，磁力搅拌30分钟使钼粉在乙醇中均匀分散。取浓度为40％双氧水，缓慢加入钼粉-醇分散体系中，持续磁力搅拌约24小时，反应产物经过静置沉淀，去除底部沉淀，保留上层清液。将上层清液置于真空干燥箱中通过室温下真空干燥除去溶剂，获得纳米氧化物粉末。将干燥获得的氧化物纳米粉末再次分散于乙醇、异丙醇或者水中，通过长时间超声分散，再经由4000rpm下离心10分钟。离心后，去除底部沉淀，留上清液，即得纳米氧化物墨水。纳米氧化物墨水浓度可以采用如下方式标定：取一定体积墨水真空干燥成粉末，称量粉末的质量，计算质量和体积的比值获得。其中，所述纳米氧化物墨水的浓度优选为8～10mg/ml。
前述纳米氧化物墨水可以通过加入醇或者水等溶剂配制成不同浓度的墨水。
进一步的，通过将金属氧化物的醇分散相(例如前述纳米氧化物墨水)与导电聚合物按照一定体积比混合获得金属氧化物-导电聚合物-醇组合物。以MoOx-PEDOT:PSS(2<x<3)复合墨水的制备为例：通过将等体积乙醇分散的MoOx墨水注入到PEDOT:PSS中，通过超声分散混合获得。
更进一步的，在应用前述金属氧化物-导电聚合物-醇组合物制备成膜，例如缓冲层时，其可以通过涂布刮刀、喷墨打印等方法在有机物表面或者ITO电极上制备获得阳极缓冲层。例如，在一些实施例中倒置结构有机光伏器件的复合空穴缓冲层可以通过旋涂的方法在有机活性层表面沉积获得。
与以真空蒸镀MoOx等金属氧化物缓冲层相比，藉由本发明工艺制备的金属氧化物-导电聚合物-醇组合物而进行的缓冲层制备工艺上与印刷法更兼容， 薄膜质量高，且获得的空穴缓冲层对大气敏感性低。而与传统的聚合物阳极缓冲层相比，本发明有更高的稳定性，且将其沉积于有机活性层表面时可避免因需要对有机光活性层表面进行紫外臭氧，氧等离子方式等的表面处理，或者对聚合物进行改性时引入表面活性剂而导致聚合物缓冲层性能下降的弊端。
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1：MoOx-(2<x<3)PEDOT:PSS-乙醇组合物的制备及在有机光伏中的应用
本实施例的具体制备工艺如下：
1.MoOx(2<x<3)的制备：取250mg大小为200目的钼粉于10ml无水乙醇中，加入0.5ml(30％)双氧水在600rpm磁力搅拌条件下进行24小时室温氧化反应，反应过程溶液的颜色逐渐由黑色迅速变为藏青色，1小时后转变为深蓝色。
2.MoOx墨水的制备：24小时后，停止反应，静置2小时后，将上层清液置于真空干燥箱中通过室温下真空干燥除去溶剂，获得纳米氧化物粉末。将干燥获得的固体粉末再次加入适量乙醇超声分散10分钟，后于4000rpm下离心10分钟。离心完，取上层蓝色清液，再次超声分散，即获得MoOx墨水。所得MoOx墨水于室温下保存，也可加入适量乙醇稀释成不同浓度的墨水备用。参阅图1a-1b可知，在MoOx墨水中金属氧化物颗粒尺寸约为5nm，且尺寸均匀，单分散性好。参阅图1c(左)所示MoOx薄膜的XPS图可知，Mo3d包含232.6eV和231.6eV两个高斯峰，均对应于Mo6+，说明MoOx中Mo的价态主要为+6价；右图显示O1s的峰位为530.5eV，对应于O2-。
3.MoOx-PEDOT:PSS-乙醇组合物墨水的制备：取浓度为8mg/ml的MoOx墨水1ml，以及1ml PEDOT:PSS(4083)混合，超声分散2分钟，即得到MoOx-PEDOT:PSS混合墨水。
4.以MoOx-PEDOT:PSS为空穴缓冲层得倒置器件的制备：倒置器件结构包括ITO阴极，ZnO阴极缓冲层，P3HT:PC61BM活性层，MoOx-PEDOT:PSS复合空穴缓冲层以及Al或Ag阳极。器件和参比器件的结构分别为：
ITO/ZnO/P3HT:PC61BM/MoOx/Ag，
ITO/ZnO/P3HT：PC61BM/MoOx-PEDOT:PSS/Ag，
ITO/ZnO/P3HT:PC61BM/e-MoO3/Ag。
在P3HT:PC61BM薄膜上旋涂MoOx空穴缓冲层(s-MoOx)，采用3500rpm转速下旋涂60s，获得的厚度约为100nm的薄膜。旋涂MoOx-PEDOT:PSS采用2000～5000rpm转速下旋涂60s，转速为2200rpm，3500rpm，5000rpm下分别得到厚度为75nm，50nm和30nm的薄膜。参阅图2a-2b可见，在P3HT:PC61BM薄膜上旋涂s-MoOx，MoOx-PEDOT:PSS薄膜后，其紫外区域和近红外区域的吸收增强，正好与s-MoOx以及PEDOT:PSS的吸收光谱位置吻合，说明s-MoOx，MoOx-PEDOT:PSS墨水可以采用溶液旋涂的方法沉积在P3HT:PC61BM表面。但请参阅图3a-3b，从薄膜的AFM图上s-MoOx和MoOx-PEDOT:PSS复合薄膜的表面粗糙度分别为2.8nm和0.8nm，可以看到通过与PEDOT:PSS复合，s-MoOx薄膜上颗粒团聚明显得到改善。而再请参阅图4及下表1可知，不同厚度MoOx-PEDOT:PSS为空穴缓冲层的倒置器件(下表MoOx-PEDOT:PSS所示)，以旋涂MoOx层为空穴缓冲层的器件(下表s-MoO3所示)与真空蒸镀MoO3为空穴缓冲层的器件(下表e-MoO3所示)具有相当的性能。
表1MoOx-PEDOT:PSS为空穴缓冲层的倒置器件与真空蒸镀MoO3为空穴缓冲层的器件的性能参数，器件结构(按照依次层叠的顺序，下同)为：ITO/ZnO/P3HT:PC61BM/MoOx-PEDOT:PSS/Ag。
Figure PCTCN2015078482-appb-000001
Figure PCTCN2015078482-appb-000002
实施例2
参考实施例1，分别制备结构如下的器件：
ITO/ZnO/P3HT:PC61BM/MoOx(2<x<3)-PEDOT:PSS/Al,
ITO/ZnO/P3HT:PC61BM/e-MoO3/Al。
请参阅图5，溶液方法制备的MoOx-PEDOT:PSS薄膜同样可以提高Al的功函数，获得与参比器件ITO/ZnO/P3HT:PC61BM/e-MoO3/Al相当的器件性能。
实施例3：ZnO-PFN-甲醇组合物的制备以及在有机光伏中的应用
ZnO纳米颗粒的制备：
取250mg大小为200目的锌粉于10ml无水乙醇中，加入0.5ml(30％)双氧水在600rpm磁力搅拌条件下进行24小时室温氧化反应。
ZnO墨水的制备：
反应停止后，静置2小时，将上层清液置于真空干燥箱中通过室温下真空干燥除去溶剂，获得纳米氧化物粉末。将干燥获得的固体粉末再次加入适量乙醇超声分散10分钟，后于4000rpm下离心10分钟。离心完，取上清液，经由超声分散，即获得颗粒尺寸为5～20nm纳米ZnO墨水。所得纳米ZnO墨水加入适量乙醇稀释成不同浓度的为10mg/ml的墨水备用。
ZnO-PFN-甲醇组合物墨水的制备：
取8ml浓度为10mg/ml的纳米ZnO墨水与2ml浓度为1mg/ml的PFN-甲醇溶液混合，经过简单超声振荡混合即获得ZnO-PFN-甲醇墨水。
ZnO-PFN-甲醇阴极缓冲层的制备：
可通过2000rpm转速下在P3HT:PC61BM薄膜上旋涂前述ZnO-PFN-甲醇墨水而获得ZnO-PFN-甲醇电子缓冲层。该电子缓冲层具有与实施例1-2相近的性能。
应当理解的是，本发明可用其他的不违背本发明的精神或主要特征的具体形式来概述。因此，无论从哪一点来看，本发明的上述实施例仅是对本发明的说明而不能限制本发明，权利要求书指出了本发明的范围，而上述的说明并未指出本发明的范围，因此在与本发明的权利要求书相当的含义和范围内的任何改变，都应认为是包括在权利要求书的范围内。

Claims (17)

  1. 一种金属氧化物-导电聚合物-醇组合物，其特征在于，包括：
    至少一种半导体金属氧化物，主要以纳米颗粒的形态均匀分散于所述组合物中；
    至少一种导电聚合物，所述导电聚合物包含至少一种共轭高分子；
    以及，包含至少一种有机醇的溶剂，用以使所述组合物呈流体状以及提高所述组合物在有机薄膜表面的浸润性。
  2. 根据权利要求1所述的金属氧化物-导电聚合物-醇组合物，其特征在于，所述半导体金属金属氧化物和导电聚合物在该组合物中的重量比为0.01-0.99：1。
  3. 根据权利要求1所述的金属氧化物-导电聚合物-醇组合物，其特征在于，所述半导体金属氧化物包括钼的氧化物、钒的氧化物、钨的氧化物、镍的氧化物、锌的氧化物、钛的氧化物中的任意一种或两种以上的组合。
  4. 根据权利要求1所述的金属氧化物-导电聚合物-醇组合物，其特征在于，所述导电聚合物包括由共轭高分子与至少一种酸性助溶剂形成的复合物。
  5. 根据权利要求4中所述的金属氧化物-导电聚合物-醇组合物，其特征在于所述的酸性助溶剂包括乙酸、丙酸、丁酸、苯甲酸、苯磺酸、对甲苯磺酸或非氟化的酸性聚合物。
  6. 根据权利要求5中所述的金属氧化物-导电聚合物-醇组合物，其特征在于，所述非氟化的酸性聚合物为聚对苯乙烯磺酸或聚(2-丙烯酰氨基-2-甲基-1-丙烷磺酸)。
  7. 根据权利要求1所述的金属氧化物-导电聚合物-醇组合物，其特征在于，所述的共轭高分子包括聚苯胺、聚吡咯、聚噻吩、聚硒吩、聚芴，聚对苯撑乙烯中的任意一种或两种以上的组合。
  8. 一种权利要求1所述的金属氧化物-导电聚合物-醇组合物的制备方法，其特征在于，包括：至少取半导体纳米金属氧化物颗粒、至少一种有机醇以及至少一种导电聚合物均匀混合，形成呈流体状的所述金属氧化物-导电聚合物-醇组合物。
  9. 根据权利要求8所述的金属氧化物-导电聚合物-醇组合物的制备方法，其特征在于，包括：
    (1)取半导体金属和/或金属氧化物粉体与双氧水在第一溶剂中混合进行氧化反应，而后将反应混合物静置，弃去沉淀物，并除去所获上清液中的溶剂，获得半导体纳米金属氧化物颗粒，所述半导体金属和/或金属氧化物粉体中所含的金属元素包括钼、钒、钨、镍、锌、钛中的任意一种或两种以上的组合；
    (2)将步骤(1)所获半导体纳米金属氧化物颗粒均匀分散于第二溶剂中，并进行离心处理，而后取上清液超声分散，形成含纳米金属氧化物的墨水；
    (3)将步骤(2)所获含纳米金属氧化物的墨水与导电聚合物均匀混合，形成所述金属氧化物-导电聚合物-醇组合物；
    其中，所述第一溶剂和第二溶剂包括水、乙醇、丙醇和异丙醇中的任一种或两种以上的组合。
  10. 根据权利要求9所述金属氧化物-导电聚合物-醇组合物的制备方法，其特征在于，包括：
    在步骤(2)中，取所述上清液加入第三溶剂，再超声分散，形成含纳米金属氧化物的墨水，再与主要由导电聚合物复合物和第四溶剂组成的导电聚合物分散液在室温下均匀混合，形成所述金属氧化物-导电聚合物-醇组合物；
    其中，所述第三溶剂和第四溶剂包括水、乙醇、丙醇和异丙醇中的任一种或两种以上的组合，但所述第三溶剂和第四溶剂不能同时为水。
  11. 根据权利要求9所述的金属氧化物-导电聚合物-醇组合物的制备方法，其特征在于，步骤(1)中用于除去所获上清液中的溶剂的方法包括真空干燥法。
  12. 根据权利要求10所述的金属氧化物-导电聚合物-醇组合物的制备方法，其特征在于，步骤(1)中用于除去所获上清液中的溶剂的方法包括真空干燥法。
  13. 一种有机电子器件，其特征在于，具有包含权利要求1所述的金属氧化物-导电聚合物-醇组合物的薄膜。
  14. 根据权利要求13所述的有机电子器件，其特征在于，所述薄膜的制成方法为：取权利要求1所述的金属氧化物-导电聚合物-醇组合物印刷成膜，其中印刷方式包括旋涂、喷墨、丝网或凹版印刷。
  15. 根据权利要求13所述的有机电子器件，其特征在于，所述有机电子器件具有电-光和/或光-电转换特性。
  16. 根据权利要求14所述的有机电子器件，其特征在于，所述有机电子器件包括太阳能电池器件或OLED器件。
  17. 根据权利要求15所述的有机电子器件，其特征在于，所述有机电子器件包括太阳能电池器件或OLED器件。
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