WO2015169243A1

WO2015169243A1 - Metal oxide-conductive polymer-alcohol composition, preparation method and use thereof

Info

Publication number: WO2015169243A1
Application number: PCT/CN2015/078482
Authority: WO
Inventors: 骆群; 马昌期
Original assignee: 深圳市博世知识产权运营有限公司
Priority date: 2014-05-07
Filing date: 2015-05-07
Publication date: 2015-11-12
Also published as: CN105098073B; CN105098073A

Abstract

Disclosed are a metal oxide-conductive polymer-alcohol composition, a preparation method and a use thereof. The composition comprises: at least one semiconductor metal oxide, which is uniformly dispersed into the composition mainly in the form of nanoparticles; at least one conductive polymer, the conductive polymer comprising at least one conjugated macromolecule; and a solvent comprising at least one organic alcohol, which is used to enable the composition to be in a fluid state and increase the wettability of the composition on a surface of an organic thin-film. In the preparation method, the nanoparticles of the semiconductor metal oxide can be directly prepared by reacting the metal or a oxide powder thereof with hydrogen peroxide, and the surface energy of the composition can be adjusted by the ratio between the metal oxide and the conductive polymer. A thin-film prepared by the deposition of the composition can be used as a buffer layer in an organic electronic device, thereby realizing the ohmic contact between a metal electrode and an organic active layer.

Description

Metal oxide-conductive polymer-alcohol composition, preparation method and application thereof

Technical field

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.

Background technique

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. For example, 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.

Currently commonly used 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. In order to obtain a high-stability full-solution processing device, 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.

More specifically, taking organic photovoltaics as an example: the composition of organic photovoltaic devices (OPVs) 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. Among them, 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. As a hole buffer layer material for organic optoelectronic devices, the solution deposition film technology is very mature. Since the inverted structure organic solar cell uses a high work function metal as an anode, it is not easily oxidized by air and has a longer life. High-function metal electrodes are also suitable for processing in air, so inverted-structured organic solar cells are generally considered compatible with the printing process. Nevertheless, since the organic active layer is highly hydrophobic and both MoO _x and PEDOT:PSS are water-soluble materials, it is still difficult to deposit an anode buffer layer on the organic active layer by a solution process. At present, the deposition of MoO _{x is} mostly achieved by vacuum evaporation, the equipment requirements are high, and the compatibility with the printing method for preparing large-area organic photovoltaic processes is poor. Depositing PEDOT:PSS on the organic thin film layer requires the addition of a surfactant to the PEDOT:PSS to modify it or to reduce the surface energy by surface treatment of the organic active layer. Late removal of surfactants is difficult. The treatment of the surface of the organic active layer with Plasma or UV O ₃ has higher requirements on the equipment, and it is possible to destroy the organic thin film to some extent and shorten the life of the device.

For example, 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. However, due to the problem that the nanoparticles are easily agglomerated and the film formation property is poor, the process requirements for preparing the electronic buffer layer by this method are required. Higher, also leads to poor repeatability of the device.

Summary of the invention

One of the objects of the present invention is to provide 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;

And 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.

Further, 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.

Further, the organic electronic device has electro-optical and/or photo-electric conversion characteristics.

Advantages of the present invention over the prior art include: 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.

DRAWINGS

1a-1b are TEM and HRTEM images of the MoO _x nanoparticles synthesized in Example 1, respectively;

1c is an XPS diagram of the MoO _x film obtained in Example 1;

2a-2b are absorption spectra of the MoO _x -PEDOT:PSS layer before and after spin coating on the P3HT:PC ₆₁ BM film 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;

4 is a JV curve of a solar cell having a different thickness of MoO _x -PEDOT:PSS as a hole buffer layer in Embodiment 1;

5 is a JV curve of an inverted device in which MoO _x -PEDOT:PSS is a hole buffer layer in Example 2.

detailed description

As previously stated, in view of the deficiencies in the prior art, one aspect of the present invention provides a metal oxide-conductive polymer-alcohol composition comprising:

And 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.

Further, 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.

Further, in the metal oxide-conductive polymer-alcohol composition, the weight ratio of the semiconductor metal oxide and the conductive polymer is 0.01-0.99:1;

Preferably, the weight ratio of the metal oxide to the polymer in the composition is 20 to 80%

Further, 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.

Further, 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.

Further, 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.

In a possible embodiment, 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.

Further, the foregoing metal oxide-conductive polymer-alcohol composition material

As an alternative embodiment, the preparation method may include:

(1) taking a metal and/or metal oxide powder and mixing it with hydrogen peroxide in a first solvent to carry out an oxidation reaction, and then allowing the reaction mixture to stand, discarding the precipitate, and adopting a method conventional in the industry, such as vacuum. The drying method removes the solvent in the obtained supernatant to obtain a nano metal oxide-containing powder, and 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;

(2) uniformly dispersing the powder obtained in the step (1) in the second solvent, and performing centrifugation, and then taking the supernatant to ultrasonically disperse to form an ink containing the nano metal oxide;

(3) 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.

Alternatively, 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.

Wherein, 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.

Further, the preparation method may further include:

In the step (2), 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. Wherein, 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.

Wherein, 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.

For example, 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.

According to still another aspect of the present invention, there is provided a film comprising any one of the foregoing metal oxides - Conductive polymer-alcohol composition.

Further, 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. Of course, 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.

In a typical implementation, the organic electronic device can be a solar cell or an OLED device.

For example, 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. For another example, 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. Wherein, the electron buffer layer may comprise the aforementioned film.

Further, 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.

Further, 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.

In a more specific embodiment, a metal oxide-conductive polymer-alcohol composition is prepared as follows:

(1) using 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. For example, in some embodiments, 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.

(2) 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. For example, 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.

Further, taking the MoO _x (2<x<3)-PEDOT:PSS-ethanol composition as an example, 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.

Further, 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. Taking the preparation of the MoO _x -PEDOT:PSS (2<x<3) composite ink as an example: by injecting an equal volume of ethanol-dispersed MoO _x ink into PEDOT:PSS, it is obtained by ultrasonic dispersion mixing.

Further, when the foregoing metal oxide-conductive polymer-alcohol composition is 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. Floor. For example, in some embodiments 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.

Compared with a metal oxide buffer layer such as MoO _{x which} is vacuum-evaporated, 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. Compared with the conventional polymer anode buffer layer, 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 technical solutions of the present invention are further described below in conjunction with the accompanying drawings and several preferred embodiments.

Example 1: Preparation of MoO _x -(2<x<3) PEDOT:PSS-Ethanol Composition and Its Application in Organic Photovoltaics

The specific preparation process of this embodiment is as follows:

1. Preparation of MoO _x (2<x<3): Take 250mg of molybdenum powder of 200 mesh size in 10ml of absolute ethanol, add 0.5ml (30%) of hydrogen peroxide, and perform room temperature oxidation reaction under magnetic stirring at 600rpm for 24 hours. The color of the reaction solution gradually changed from black to navy, and turned dark blue after 1 hour.

2. Preparation of MoO _x ink: After 24 hours, the reaction was stopped, and after standing for 2 hours, 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 upper blue serum was taken and ultrasonically dispersed again to obtain MoO _x ink. The obtained MoO _x ink is stored at room temperature, and may be diluted with an appropriate amount of ethanol to prepare inks of different concentrations for use. Referring to Figures 1a-1b, 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. Referring to the XPS diagram of the MoO _x film shown in Figure 1c (left), 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- .

3. Preparation of MoO _x -PEDOT:PSS-ethanol composition ink: 1 ml of MoO _x ink at a concentration of 8 mg/ml, and 1 ml of PEDOT:PSS (4083) were mixed and ultrasonically dispersed for 2 minutes to obtain MoO _x -PEDOT: PSS mixed ink.

4. Preparation of 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. Referring to Figures 2a-2b, 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. However, referring to Figures 3a-3b, 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. Referring to 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.

Table 1 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.

Example 2

Referring to Example 1, the following structures were prepared:

ITO/ZnO/P3HT: PC ₆₁ BM/MoO _x (2<x<3)-PEDOT:PSS/Al,

ITO/ZnO/P3HT: PC ₆₁ BM/e-MoO ₃ /Al.

Referring to FIG. 5, 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.

Example 3: Preparation of ZnO-PFN-methanol composition and its application in organic photovoltaics

Preparation of ZnO nanoparticles:

250 mg of zinc powder having a size of 200 mesh was placed in 10 ml of absolute ethanol, and 0.5 ml (30%) of hydrogen peroxide was added thereto to carry out a room temperature oxidation reaction under magnetic stirring at 600 rpm for 24 hours.

Preparation of ZnO ink:

After the reaction was stopped, 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.

Preparation of ZnO-PFN-methanol composition ink:

8 ml of nano-ZnO ink with a concentration of 10 mg/ml was mixed with 2 ml of a PFN-methanol solution having a concentration of 1 mg/ml, and ZnO-PFN-methanol ink was obtained by simple ultrasonic vibration mixing.

Preparation of ZnO-PFN-methanol cathode buffer layer:

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.

It is understood that the invention may be embodied in other specific forms without departing from the spirit and scope of the invention. Therefore, the above-described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and the scope of the invention Any changes which come within the meaning and range of the claims are intended to be included within the scope of the appended claims.

Claims

A metal oxide-conductive polymer-alcohol composition characterized by 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;

And 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 metal oxide-conductive polymer-alcohol composition according to claim 1, wherein the weight ratio of the semiconductor metal metal oxide and the conductive polymer in the composition is from 0.01 to 0.99:1.
The metal oxide-conductive polymer-alcohol composition according to claim 1, wherein the semiconductor metal oxide comprises an oxide of molybdenum, an oxide of vanadium, an oxide of tungsten, an oxide of nickel, Any one or a combination of two or more of an oxide of zinc and an oxide of titanium.
The metal oxide-conductive polymer-alcohol composition according to claim 1, wherein the conductive polymer comprises a composite of a conjugated polymer and at least one acidic co-solvent.
The metal oxide-conductive polymer-alcohol composition according to claim 4, wherein said acidic co-solvent comprises acetic acid, propionic acid, butyric acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid or Non-fluorinated acidic polymer.
The metal oxide-conductive polymer-alcohol composition according to claim 5, wherein the non-fluorinated acidic polymer is poly-p-styrenesulfonic acid or poly(2-acrylamido-2) -Methyl-1-propanesulfonic acid).
The metal oxide-conductive polymer-alcohol composition according to claim 1, wherein the conjugated polymer comprises polyaniline, polypyrrole, polythiophene, polyselenophene, polyfluorene, polyparaphenylene. Any one or a combination of two or more of ethylene.
A method for preparing a metal oxide-conductive polymer-alcohol composition according to claim 1, 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.
The method for preparing a metal oxide-conductive polymer-alcohol composition according to claim 8, comprising:

(1) taking a semiconductor metal and/or metal oxide powder and mixing it with hydrogen peroxide in a first solvent to carry out an oxidation reaction, and then allowing the reaction mixture to stand, discarding the precipitate, and removing the solvent in the obtained supernatant to obtain a semiconductor nano metal oxide particle, the metal element contained in the semiconductor metal and/or metal oxide powder comprising any one or a combination of two or more of molybdenum, vanadium, tungsten, nickel, zinc, titanium;

(2) uniformly dispersing the semiconductor nano metal oxide particles obtained in the step (1) in a second solvent, and performing centrifugation, and then taking the supernatant to ultrasonically disperse to form an ink containing the nano metal oxide;

(3) uniformly mixing the nano metal oxide-containing ink obtained in the step (2) with the conductive polymer to form the metal oxide-conductive polymer-alcohol composition;

Wherein the first solvent and the second solvent include any one or a combination of two or more of water, ethanol, propanol and isopropanol.
The method of preparing a metal oxide-conductive polymer-alcohol composition according to claim 9, comprising:

In the step (2), the supernatant is added to a third solvent, and then ultrasonically dispersed to form an ink containing a nano metal oxide, and then dispersed with a conductive polymer mainly composed of a conductive polymer composite and a fourth solvent. The liquid is uniformly mixed at room temperature to form the metal oxide-conductive polymer-alcohol composition;

Wherein the third solvent and the fourth solvent include any one or a combination of two or more of water, ethanol, propanol and isopropanol, but the third solvent and the fourth solvent are not simultaneously water.
The method of producing a metal oxide-conductive polymer-alcohol composition according to claim 9, wherein the method for removing the solvent in the obtained supernatant in the step (1) comprises a vacuum drying method.
The method of producing a metal oxide-conductive polymer-alcohol composition according to claim 10, wherein the method for removing the solvent in the obtained supernatant in the step (1) comprises a vacuum drying method.
An organic electronic device comprising a film comprising the metal oxide-conductive polymer-alcohol composition of claim 1.
The organic electronic device according to claim 13, wherein the film is formed by printing the metal oxide-conductive polymer-alcohol composition according to claim 1 into a film, wherein the printing method comprises Spin coating, inkjet, screen or gravure printing.
The organic electronic device according to claim 13, wherein the organic electronic device has electro-optical and/or photo-electric conversion characteristics.
The organic electronic device according to claim 14, wherein the organic electronic device comprises a solar cell device or an OLED device.
The organic electronic device according to claim 15, wherein the organic electronic device comprises a solar cell device or an OLED device.