WO2014067233A1

WO2014067233A1 - Preparation method for high-conductivity organic transparent conductive film

Info

Publication number: WO2014067233A1
Application number: PCT/CN2013/001219
Authority: WO
Inventors: 刘星元; 郭晓阳
Original assignee: 中国科学院长春光学精密机械与物理研究所
Priority date: 2012-10-30
Filing date: 2013-10-11
Publication date: 2014-05-08
Also published as: CN103794728A

Abstract

Provided is a preparation method for a high-conductivity organic transparent conductive film.An organic micromolecular or polymer semiconductor material is used as a dielectric layer (200, 400) to prepare a transparent conductive film of a dielectric/metal/dielectric multilayer structure, so that the light transmittance of a visible region and an ultra-low area of resistance of less than 10 Ω/口 can be achieved, the selection of the dielectric material in the dielectric/metal/dielectric multilayer structure being greatly extended, and a large number of n-type and p-type organic transparent conductive films with different properties being achieved.The transparent conductive film has the potential of being applied to the field of optoelectronic devices such as thin film solar batteries, and organic light-emitting diodes, and the transparent conductive film based on an organic semiconductor material is more beneficial for achieving a high-performance flexible transparent conductive film.

Description

Method for preparing highly conductive organic transparent conductive film

The invention relates to the technical field of transparent conductive film materials, and in particular to a method for preparing a highly conductive organic transparent conductive film. Background technique

Transparent conductive film is an important photoelectric functional film, which is widely used in the fields of liquid crystal display, organic light emitting diode, touch screen, thin film solar cell and the like. The transparent conductive film currently reported mainly includes a transparent conductive oxide film doped with ln ₂ 0 ₃ , Sn0 ₂ and ZnO as a host material (Nature Mater. 2005, 4, 864-868; Sol. Energy Mater. Sol Cells 2010, 94, 2328-2331 ; ^/. Phys. Lett. 2010, 96, 133506 ) , polystyrene derivative poly(3,4-ethylenedioxythiophene) (PEDOT) doped polystyrene sulfonate Conductive polymer film represented by acid (PSS) U. Mater. Chem. 2005, 15, 2077-2088; Adv. Funct. Mater. 2004, 14, 615-622), represented by carbon nanotubes and graphene Carbon-based transparent conductive film Science 2004, 305, 1273-1276; ACS Nano 2010, 4, 5263-5268), and metal nanostructured transparent conductive film typified by metal nanowires and metal nanogrids (Nano Lett. 2008) , 8, 689-692; Adv. Mater. 2010, 22, 3558-3563 ). The most commonly used transparent conductive film is an indium tin oxide (ITO) film, which has high visible light transmittance and low resistivity, and is often used in optoelectronic devices such as organic solar cells and organic light emitting diodes. Transparent electrode. With the advancement of technology, the future development trend of optoelectronic devices is low cost, light weight and flexibility, while the traditional ITO film can not meet the requirements of preparing low-cost flexible devices. This is mainly because the ITO film is brittle, and the sheet resistance increases sharply when subjected to force bending. In addition, due to the rare indium element, the preparation cost of ITO increases year by year. Therefore, the development of a low-cost and bending-resistant transparent conductive film will play a beneficial role in promoting the development of photovoltaic devices in the future. Confirmation The dielectric/metal/dielectric multilayer structure can achieve high conductivity and high transmittance in the visible region by adjusting the thickness of the metal and dielectric layers, and the high electrical conductivity of the multilayer structure is mainly affected by the thickness of the metal layer. Ultra low surface resistance of less than 10 Ω/□ can be achieved with a metal layer of appropriate thickness. This structure was first applied to increase the conductivity of a transparent conductive oxide film. A transparent conductive film of ITO/Ag/ITO structure with a total thickness of not more than 100 nm can achieve a surface resistance of less than 5 Ω/□ and a visible light area of more than 85. % transmittance Opt. Commun. 2009, 282, 574-578). The medium/metal/dielectric multilayer structures reported so far use inorganic semiconductor materials as dielectric layers.

Compared with inorganic semiconductor materials, organic semiconductor materials have a wide range of materials, light weight, low cost, and resistance to bending, and are good low-cost flexible materials. However, the carrier mobility of the organic semiconductor thin film is usually very low, generally in the order of lO^-lO^cr^V- ¹ , and the carrier concentration is also much lower than that of the inorganic semiconductor film, so most organic semiconductor thin films The conductivity is very poor. At present, the transparent conductive film based on organic materials has an optimum sheet resistance of about 150 Ω/D iAdv. Fund. Mater. 201 1 , 21 , 1076-1081 when the visible light transmittance is greater than 85%. Performance is far from meeting the requirements of optoelectronic devices for transparent electrodes. Summary of the invention

In order to solve the problem that the performance of the organic material-based transparent conductive film in the prior art cannot meet the requirements of the photovoltaic device, the present invention particularly provides a dielectric/metal/dielectric multilayer structure using an organic semiconductor material as a dielectric layer. A method for preparing a highly conductive organic transparent conductive film without indium and being flexible.

The technical solution of the method for preparing the highly conductive organic transparent conductive film material of the present invention is as follows:

A method for preparing a highly conductive organic transparent conductive film, comprising the steps of:

Step i, preparing a first dielectric layer on a rigid or flexible planar substrate; Step ii, preparing a metal layer on the first dielectric layer;

Step i i i, preparing a second dielectric layer on the metal layer;

The materials of the first dielectric layer and the second dielectric layer are respectively: any one of organic semiconductor materials, or a mixture of any of a plurality of organic semiconductor materials.

In the above technical solution, the organic semiconductor material comprises an organic small molecule semiconductor material and a polymer semiconductor material.

In the above technical solution, when the first dielectric layer and the second dielectric layer are a mixture of two organic semiconductor materials, the mass mixing ratio of the two materials is 1:99-1:4.

In the above technical solution, when the first dielectric layer and the second dielectric layer are mixed with three or more kinds of organic semiconductor materials, each of the materials has a mass of at least 1% of the total mass of the mixture.

In the above technical solution, the thickness of the first dielectric layer and the second dielectric layer are respectively 10-300 nm.

In the above technical solution, the materials of the first dielectric layer and the second dielectric layer are respectively any one of the following materials or mixtures: polyvinyl carbazole (PVK), OXD-7, pentacene, copper phthalocyanine (CuPc), a mixture of poly 3 hexylthiophene (P3HT) and OXD-7, a mixture of PEDOT and PSS, a mixture of 2T-NATA and F4-TCNQ, a mixture of m-MTDATA and F4-TCNQ, P3HT: OXD-7: Mixture of PVK or pentacene: OXD-7: m-MTDATA: a mixture of F4-TCNQ, and the like.

In the above technical solution, when the first dielectric layer and the second dielectric layer are prepared by spin coating, the spin coating speed is 500-3000 rpm, respectively, and the spin coating time is 1-2 minutes, respectively.

In the above technical solution, the metal layer material is Ag, Au, Pt or Cu; and the metal layer has a thickness of 8-30 nm.

In the above technical solution, the metal layer is prepared by electron beam evaporation, thermal evaporation, magnetron sputtering or ion sputtering. In the above technical solution, in the step i, the rigid planar substrate is glass, quartz, metal, inorganic crystal or semiconductor; and the flexible planar substrate is plastic, paper or cloth.

The highly conductive organic transparent conductive film of the present invention has the following beneficial effects:

The highly conductive organic transparent conductive film of the present invention is a transparent conductive film prepared by using an organic semiconductor material as a dielectric layer by using a dielectric/metal/dielectric structure, which can not only greatly improve the electrical conductivity of the organic transparent conductive film, but also expand the medium. The choice of the dielectric material of the metal/medium structure transparent conductive film enables a large number of n-type and p-type organic transparent conductive films having different photoelectric properties. Such an organic transparent conductive film can be prepared for use as an electrode of a photovoltaic device on a variety of rigid or flexible substrates.

The highly conductive organic transparent conductive film of the present invention has high visible light transmittance and low surface resistance, and has potential for application in photovoltaic devices such as thin film solar cells and organic light emitting diodes. DRAWINGS

Fig. 1 is a schematic view showing the structure of a dielectric/metal/dielectric multilayer transparent conductive film based on an organic material.

Figure 2 is a transmission spectrum of Examples 1, 2, 3, 4 and Comparative Example 1. The structures of Examples 1, 2, 3, and 4 are PVK C 35 nm) / Ag (12 nm) / PVK ( 35 nm) (curve 1 ), PVK (40 nm) / Ag (12 nm) / PVK ( 40 nm) (curve 2), PVK (45 nm) / Ag (12 nm) / PVK (45 nm) (curve 3 ), PVK ( 55 nm) / Ag (12 nm) / PVK ( 55 nm) (curve 4 ). Comparative Example I is a 12 nm metal Ag film (curve 5).

Fig. 3 is a transmittance spectrum of Example 5 and Comparative Example II. The structure of Example 5 was PVK (45 nm) / Au (8 nm) PVK (45 nm) (curve 1), and the comparative example Π was a 8 nm metal Au film (curve 2).

4 is a current-voltage characteristic curve of Example 41 and Comparative Example XD, specifically, an example. 13 is a current-voltage characteristic curve of a polymer solar cell prepared by an anode (Example 41) and a polymer solar cell prepared by using ITO as an anode (Comparative Example ΧΠ). The device structure of Example 41 is PVK (35 nm) / Ag (15 nm) / PEDOT: PSS (35 nm) / P3HT: PCBM (mass ratio 1:1, 100 nm) / LiF (1 nm) / Al (100 nm) (curve 1), the device structure of the comparative ΧΠ is ITO/PEDOT:PSS (mass ratio 1:6, 35 nm)/P3HT:PCBM (mass ratio 1:1,100 nm)/LiF ( 1 nm) / Al (100 nm) (curve 2). detailed description

The invention provides a method for preparing a highly conductive organic transparent conductive film material, and the structure of the transparent conductive film involved is as shown in FIG. 1 - the flat substrate 100 is glass, plastic, quartz, semiconductor, A rigid or flexible planar substrate of inorganic crystals, metal, paper, cloth, etc.

The material of the first dielectric layer 200 is an organic semiconductor material, or a mixture of a plurality of organic semiconductor materials, wherein the organic semiconductor material includes an organic small molecule semiconductor material and a polymer semiconductor material. When the mixture is of two materials, the mass ratio of the two materials is 1:99-1:4; when the mixture is three or more materials, each of the materials has a mass of at least 1% of the total mass of the mixture; It is 10-300 nm.

The metal layer 300 is made of a metal material such as Ag, Au, Pt or Cu, and has a thickness of 8-30 nm _;

The metal layer 300 is prepared by any one of electron beam evaporation, thermal evaporation, magnetron sputtering, or ion sputtering.

The material of the second dielectric layer 400 is an organic semiconductor material, or a mixture of a plurality of organic semiconductor materials, wherein the organic semiconductor material comprises an organic small molecule semiconductor material and a polymer semiconductor material, and when the mixture is two materials, the two materials are The mass mixing ratio is 1:99-1:4; when the mixture is three or more materials, each of the materials has a mass of at least 1% of the total mass of the mixture; 10-300nm.

When the above organic small molecule semiconductor material is an organic small molecule semiconductor material such as CuPc, pentacene, OXD-7, m-MTDATA, F4-TCNQ, 2T-NATA, etc., the preparation method of the dielectric layer based on the organic small molecule semiconductor material is Solution spin coating or thermal evaporation.

When the polymer semiconductor material is a polymer semiconductor material such as PVK, P3HT or PEDOT:PSS, the preparation method of the dielectric layer based on the polymer semiconductor material is a solution spin coating process; in the above solution spin coating process, the solution concentration is 10 -30 mg / ml. The steps of the method for preparing the highly conductive organic transparent conductive film of the present invention are as follows:

Step 1), preparing a first dielectric layer 200 on the rigid or flexible planar substrate 100;

Step 2), preparing a metal layer 300 on the first dielectric layer 200;

Step 3), preparing a second dielectric layer 400 on the metal layer 300;

The materials of the first dielectric layer 200 and the second dielectric layer 400 are respectively an organic semiconductor material or a mixture of a plurality of organic semiconductor materials; the organic semiconductor material comprises an organic small molecule semiconductor material and a polymer. semiconductors. Specifically, the method for preparing the highly conductive organic transparent conductive film of the present invention:

The first dielectric layer 200, the metal layer 300, and the second dielectric layer 400 are sequentially formed on the planar substrate 100 to form a first dielectric layer 200 having a thickness of 10 to 300 nm, a metal layer 300 and a 10-300 of 8-30 nm, respectively. a second dielectric layer 400 of nm, wherein the first dielectric layer 200 and the second dielectric layer 400 may be prepared using the same or different materials;

The above planar substrate 100 is a rigid or flexible material such as glass, plastic, quartz, semiconductor, inorganic crystal, metal, paper or cloth; The first dielectric layer 200 and the second dielectric layer 400 are made of chlorobenzene-dissolved PVK, chlorobenzene-dissolved OXD-7, PEDOT:PSS, chlorobenzene-dissolved P3HT:OXD-7 or chlorobenzene-dissolved P3HT: OX D-7: solution of materials such as PVK, and thermally evaporated CuPc, pentacene, OXD-7, m-MTDATA: F4-TCNQ, 2T-NATA: F4-TCNQ or pentacene: OXD-7:m- MTDATA: organic small molecular semiconductor materials such as F4-TCNQ;

The metal layer 300 is made of a metal material such as Ag, Au, Pt or Cu, and the metal layer 300 is prepared by electron beam evaporation, thermal evaporation, magnetron sputtering or ion sputtering. In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The following are specific descriptions of Examples 1 to 41 and Comparative Examples I to ::

Example 1

The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a glass substrate. The dissolved 10 mg/ml polymer PVK solution was evenly dropped on a glass substrate, and spin-coated at 3000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 35 nm, which was then coated with the first The glass substrate of the dielectric layer 200 is placed in an electron beam coater to evacuate, and when the degree of vacuum reaches 1.2 χ10· ³ Pascal, the metal Ag of 12 nm thickness is evaporated as the metal layer 300, and then the first dielectric layer 200 and the metal layer are carried. The glass substrate of 300 was taken out and placed on the carrier of the homogenizer, and the dissolved 10 mg/ml polymer PVK solution was evenly dropped on the metal layer 300, and spin-coated at 3000 rpm for 1 minute to obtain a thickness. A second dielectric layer 400 of 35 nm finally forms a multilayer transparent conductive film having a structure of PVK (35 nm) / Ag (12 nm) / PVK (35 nm).

Example 2: The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a glass substrate. The dissolved 10 mg/ml polymer PVK solution was evenly dropped on a glass substrate, and spin-coated at 2000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 40 nm, which was then coated with the first The glass substrate of the dielectric layer 200 is placed in an electron beam coater to evacuate, and when the degree of vacuum reaches 1.2 Χ 10· ³ Pascal, the metal Ag of 12 nm thickness is evaporated as the metal layer 300, and then the first dielectric layer 200 and the metal are provided. The glass substrate of the layer 300 was taken out and placed on a carrier of the homogenizer, and the dissolved 10 mg/ml polymer PVK solution was evenly dropped on the metal layer 300, and spin-coated at 2000 rpm for 1 minute to obtain A second dielectric layer 400 having a thickness of 40 nm finally forms a multilayer transparent conductive film having a structure of PVK (40 nm) / Ag (12 nm) / PVK (40 nm). The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a glass substrate. The dissolved 10 mg/ml polymer PVK solution was evenly dropped on a glass substrate, and spin-coated at 1000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 45 nm, which was then coated with the first The glass substrate of the dielectric layer 200 is placed in an electron beam coater to evacuate, and when the degree of vacuum reaches 1.2 χ 10· ³ Pascal, the metal Ag of 12 nm thickness is evaporated as the metal layer 300, and then the first dielectric layer 200 and the metal are provided. The glass substrate of layer 300 was taken out and placed on a carrier of the homogenizer, and the dissolved 10 mg/ml polymer PVK solution was evenly dropped on the metal layer 300, and spin-coated at 1000 rpm for 1 minute to obtain The second dielectric layer 400 having a thickness of 45 nm finally forms a multilayer transparent conductive film having a structure of PVK (45 nm) / Ag (12 nm) / PVK (45 nm). The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a glass substrate. The dissolved 10 mg/ml polymer PVK solution was evenly dropped on a glass substrate, and spin-coated at 500 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 55 nm, and then The glass substrate coated with the first dielectric layer 200 is placed in an electron beam coater to evacuate, and when the degree of vacuum reaches 1.2 χ 10· ³ Pascal, the metal Ag of 12 nm thickness is evaporated as the metal layer 300, and then the first layer is provided. The glass substrate of the dielectric layer 200 and the metal layer 300 is taken out and placed on the carrier of the homogenizer, and the dissolved 10 mg/ml polymer PVK solution is evenly dropped on the metal layer 300, and is rotated at a speed of 500 rpm. After coating for 1 minute, a second dielectric layer 400 having a thickness of 55 nm was obtained, and finally a multilayer transparent conductive film having a structure of PVK (55 nm) / Ag (12 nm) / PVK (55 nm) was formed.

Comparative Example I :

The planar substrate 100 is cleaned and dried, and then placed in an electron beam coater to evacuate. When the degree of vacuum reaches 1.2×10 ⁻³ Pascal, the metal Ag having a thickness of 12 nm is evaporated; the planar substrate 100 is a glass substrate. The planar substrate 100 is cleaned and dried, and then placed on a gluer tray; the planar substrate 100 is a glass substrate. The dissolved 15 mg/ml polymer PVK solution was evenly dropped on a glass substrate, and spin-coated at 3000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 45 nm, which was then coated with the first The glass substrate of the dielectric layer 200 is placed in a thermal evaporation apparatus to evacuate, and when the degree of vacuum reaches 4.0 x 10 - ⁴ Pascals, the metal Au of 8 nm thickness is evaporated as the metal layer 300, and then the first dielectric layer 200 and the metal layer 300 are carried. The glass substrate was taken out and placed on the carrier of the homogenizer. The dissolved 15 mg/ml polymer PVK solution was evenly dropped on the metal layer 300, and spin-coated at 3000 rpm for 1 minute to obtain a thickness of A second dielectric layer 400 of 45 nm finally forms a multilayer transparent conductive film having a structure of PVK (45 nm) / Au (8 nm) / PVK (45 nm).

Comparative Example II:

The planar substrate 100 is cleaned and dried, and then placed in a thermal evaporation coating machine to evacuate. When the degree of vacuum reaches 4.0 χ 10· ⁴ Pascal, the metal Au of 8 nm thickness is evaporated; the planar substrate 100 is a glass substrate. Example 6 The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a quartz substrate. The dissolved 20 mg/ml polymer PVK solution was evenly dropped on a quartz substrate, and spin-coated at 800 rpm for 1.5 minutes to obtain a first dielectric layer 200 having a thickness of 150 nm, which was then coated with the first The quartz substrate of the dielectric layer 200 is placed in a magnetron sputtering coater to evacuate, and a metal thickness of 15 nm is sputtered as a metal layer 300 at a vacuum of 1 Pascal, followed by a first dielectric layer 200 and a metal layer. The quartz substrate of 300 was taken out and placed on the carrier of the homogenizer, and the dissolved 30 mg/ml polymer PVK solution was evenly dropped on the metal layer 300, and spin-coated at 500 rpm for 2 minutes to obtain a thickness. As a second dielectric layer of 300 nm, a multilayer transparent conductive film with a structure of PVK (150 nm) / Cu (15 nm) / PVK (300 nm) is finally formed.

Example 7

The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a quartz substrate. The dissolved 20 mg/ml P3HT:OXD-7 (mass ratio 1:9) mixed solution was evenly dropped on a quartz substrate, and spin-coated at 2000 rpm for 1 minute to obtain a thickness of 85 nm. a dielectric layer 200, and then the quartz substrate coated with the first dielectric layer 200 is placed in a magnetron sputtering coating machine to evacuate, and a metal thickness of 15 nm is sputtered as a metal layer 300 at a vacuum of 1 Pascal. The quartz substrate with the first dielectric layer 200 and the metal layer 300 is taken out and placed on a homogenizer holder, and the dissolved 20 mg/ml P3HT:OXD-7 (mass ratio 1:9) mixed solution is dissolved. Evenly dripping on the metal layer 300, spin coating at 2000 rpm for 1 minute to obtain a second dielectric layer 400 having a thickness of 85 nm, and finally forming a structure of P3HT: OXD-7 (85 nm) / Cu (15 nm) ) / P3HT: OXD-7 (85 nm) multilayer transparent conductive film. The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a quartz substrate. Dip the PEDOT: PSS (mass ratio 1:6) solution evenly onto the quartz substrate at 500 rpm. Spinning at a minute speed for 2 minutes, a first dielectric layer 200 having a thickness of 65 nm was obtained, and then the quartz substrate coated with the first dielectric layer 200 was placed in a magnetron sputtering coater to evacuate at a vacuum of 1 Pascal. When a metal Cu of 15 nm thickness is sputtered as the metal layer 300, the quartz substrate with the first dielectric layer 200 and the metal layer 300 is taken out and placed on the carrier of the homogenizer, PEDOT: PSS (mass ratio is 1) :6) The solution was evenly dropped on the metal layer 300, and spin-coated at 500 rpm for 2 minutes to obtain a second dielectric layer 400 having a thickness of 65 nm, and finally formed into a structure of PEDOT: PSS (65 nm) / Cu ( 15 nm) / PEDOT: PSS (65 nm) multilayer transparent conductive film.

Example 9

The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a quartz substrate. The dissolved 30 mg/ml PVK solution was evenly dropped on a quartz substrate and spin-coated at 500 rpm for 2 minutes to obtain a first dielectric layer 200 having a thickness of 300 nm, which was then coated with a first dielectric layer. The quartz substrate of 200 was placed in a magnetron sputtering coater to evacuate, and a metal of Cu of 15 nm thickness was sputtered as a metal layer 300 at a vacuum of 1 Pascal, and then with the first dielectric layer 200 and the metal layer 300. The quartz substrate was taken out and placed on the carrier of the homogenizer, and a PEDOT:PSS (mass ratio 1:10) solution was evenly dropped on the metal layer 300, and spin-coated at 1000 rpm for 1.5 minutes to obtain a thickness of 55. The second dielectric layer 400 of nm finally forms a multilayer transparent conductive film having a structure of PVK (300 nm) / Cu (15 nm) / PEDOT: PSS (55 nm).

Comparative ratio m:

The planar substrate 100 is cleaned and dried, and then placed in a magnetron sputtering coater to evacuate a metal having a thickness of 15 nm at a vacuum of 1 Pascal; the planar substrate 100 is a quartz substrate.

Example 10

The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a semiconductor silicon substrate. Mix the dissolved 15 mg/ml P3HT:OXD-7 (mass ratio 1:8) The solution was uniformly dropped on the semiconductor silicon substrate, spin-coated at 2500 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 45 nm, and then 30 nm was prepared on the first dielectric layer 200 by ion sputtering deposition technique. A metal Au of a thickness is used as the metal layer 300, and then the semiconductor silicon substrate with the first dielectric layer 200 and the metal layer 300 is placed on the carrier of the homogenizer, and the dissolved 15 mg/ml of P3HT:OXD-7 ( The mass ratio was 1:8) The mixed solution was uniformly dropped on the metal layer 300, and spin-coated at 2500 rpm for 1 minute to obtain a second dielectric layer 400 having a thickness of 45 nm, and finally the structure was P3HT: OXD-7. (45 nm) / Au (30 nm) / P3HT: OXD-7 (45 nm) multilayer transparent conductive film. The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a semiconductor silicon substrate. The PEDOT: PSS (mass ratio 1:4) solution was evenly dropped on a semiconductor silicon substrate, and spin-coated at 3000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 10 nm, and then ion sputtering was used. The deposition technique prepares a metal Au of 30 nm thickness as the metal layer 300 on the first dielectric layer 200, and then places the semiconductor silicon substrate with the first dielectric layer 200 and the metal layer 300 on the carrier of the homogenizer, and puts PEDOT: The PSS (mass ratio 1:4) solution was evenly dropped on the metal layer 300, and spin-coated at 3000 rpm for 1 minute to obtain a second dielectric layer 400 having a thickness of 10 nm, and finally the structure was PEDOT: PSS ( lO nm) /Au (30 nm) / PEDOT: PSS (10 nm) multilayer transparent conductive film.

Example 12:

The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a semiconductor silicon substrate. The dissolved 10 mg/ml polymer PVK solution was evenly dropped on a semiconductor silicon substrate, and spin-coated at 3000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 35 nm, and then ion-splashing. A sputtering deposition technique is used to prepare a metal Au having a thickness of 30 nm as the metal layer 300 on the first dielectric layer 200, and then a semiconductor silicon substrate having the first dielectric layer 200 and the metal layer 300. Placed on the mixer bracket, evenly pour the PEDOT: PSS (mass ratio 1:6) solution onto the metal layer 300, spin it at 2300 rpm for 1 minute to obtain a second thickness of 35 nm. The dielectric layer 400 finally forms a multilayer transparent conductive film having a structure of PVK (35 nm) / Au (30 nm) / PEDOT: PSS (35 nm).

Comparative Example IV:

After the planar substrate 100 is cleaned and dried, a metal Au having a thickness of 30 nm is prepared by an ion sputtering deposition technique; the planar substrate 100 is a semiconductor silicon substrate.

Example 13

The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a plastic substrate. The dissolved 10 mg/ml polymer PVK solution was evenly dropped on a plastic substrate, and spin-coated at 3000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 35 nm, which was then coated with the first The plastic substrate of the dielectric layer 200 is placed in a thermal evaporation coating machine to evacuate, and when the degree of vacuum reaches 4.0 χ 1 (Τ ⁴ Pascals, 15 nm of metal Ag is evaporated as the metal layer 300, and then the first dielectric layer 200 is The plastic substrate of the metal layer 300 was taken out and placed on the carrier of the homogenizer, and the PEDOT:PSS (mass ratio 1:6) solution was evenly dropped on the metal layer 300, and spin-coated at 2300 rpm for 1 minute. A second dielectric layer 400 having a thickness of 35 nm is obtained, and finally a multilayer flexible transparent conductive film having a structure of PVK (35 nm) / Ag (15 nm) / PEDOT: PSS (35 nm) is formed.

Example 14

The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a plastic substrate. The dissolved 10 mg/ml P3HT:OXD-7 (mass ratio 1:4) mixed solution was evenly dropped on a plastic substrate, and spin-coated at 2000 rpm for 1 minute to obtain a thickness of 25 nm. a dielectric layer 200, then the plastic substrate coated with the first dielectric layer 200 is placed in a thermal evaporation coating machine to evacuate, and when the degree of vacuum reaches 4.0 χ 10 ^-4 Pascal, the metal Ag of 15 nm thickness is evaporated as the metal layer 300. The plastic substrate with the first dielectric layer 200 and the metal layer 300 is then taken out and placed on a homogenizer holder, and the dissolved 10 mg/ml P3HT:OXD-7 (mass ratio 1:4) is mixed. The solution was uniformly dropped on the metal layer 300, and spin-coated at 2000 rpm for 1 minute to obtain a second dielectric layer 400 having a thickness of 25 nm, and finally a structure of P3HT: OXD-7 (25 nm) / Ag (15) was formed. Nm)/P3HT: OXD-7

Multilayer flexible transparent conductive film (25 nm).

Example 15

The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a plastic substrate. PEDOT: PSS (mass ratio 1:6) solution was evenly dropped on a plastic substrate, and spin-coated at 2300 rpm for 1 minute to obtain a first dielectric layer having a thickness of 35 nm, which was then coated with the first medium. The plastic substrate of the layer 200 is placed in a thermal evaporation coating machine to evacuate, and when the degree of vacuum reaches 4.0 χ 10· ⁴ Pascal, the metal Ag of 15 nm thickness is evaporated as the metal layer 300, and then the first dielectric layer 200 and the metal layer are carried. The plastic substrate of 300 was taken out and placed on the carrier of the homogenizer, and the PEDOT: PSS (mass ratio 1:6) solution was evenly dropped on the metal layer 300, and spin-coated at 1000 rpm for 1 minute to obtain a thickness. As a second dielectric layer 400 of 45 nm, a multilayer flexible transparent conductive film having a structure of PEDOT: PSS (35 nm) / Ag (15 nm) / PEDOT: PSS (45 nm) is finally formed.

Comparative example V:

The planar substrate 100 is cleaned and dried, and then placed in a thermal evaporation coating machine to evacuate. When the degree of vacuum reaches 4.0 χ 10· ⁴ Pascal, the metal Ag of 15 nm thickness is evaporated; the planar substrate 100 is a plastic substrate. Example 16:

After the planar substrate 100 is cleaned and dried, 30 nm thick CuPc is sequentially prepared as the first dielectric layer 200, 30 nm thick Au is used as the metal layer 300, and 30 nm thick CuPc is used as the second dielectric layer 400, and finally the structure is formed. Multilayer transparent conductive film of CuPc (30 nm) / Au (30 nm) / CuPc (30 nm). Wherein the planar substrate 100 is a glass substrate; the first dielectric layer 200, the metal layer 300, and the second The dielectric layers 400 are all prepared by thermal evaporation.

Example 17

After the planar substrate 100 is cleaned and dried, 75 nm thick pentacene is sequentially prepared as the first dielectric layer 200, 30 nm thick Au is used as the metal layer 300, and 95 nm thick pentacene is used as the second dielectric layer 400. Finally, a multilayer transparent conductive film having a structure of pentacene (75 nm) / Au (30 nm) / pentacene (95 nm) was formed. The planar substrate 100 is a glass substrate; the first dielectric layer 200, the metal layer 300 and the second dielectric layer 400 are all prepared by thermal evaporation.

Example 18

The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a glass substrate. The dissolved 20 mg/ml organic OXD-7 solution was evenly dropped on a glass substrate, and spin-coated at 800 rpm for 1.5 minutes to obtain a first dielectric layer 200 having a thickness of 150 nm, which was then coated with The glass substrate of a dielectric layer 200 is placed in a thermal evaporation apparatus to evacuate, and when the degree of vacuum reaches 4.0 χ 10· ⁴ Pascal, 30 nm thick Au is evaporated as the metal layer 300, and then the first dielectric layer 200 and the metal layer 300 are carried. The glass substrate was taken out and placed on the carrier of the homogenizer. The dissolved 20 mg/ml organic OXD-7 solution was evenly dropped on the metal layer 300, and spin-coated at 800 rpm for 1 minute to obtain a thickness. As a second dielectric layer 400 of 150 nm, a multilayer transparent conductive film having a structure of OXD-7 (150 nm) / Au (30 nm) / OXD-7 (150 nm) is finally formed.

Comparative example VI:

The planar substrate 100 is cleaned and dried, and then placed in a thermal evaporation apparatus to evacuate. When the degree of vacuum reaches 4.0 Χ 10· ⁴ Pascal, the Au film is evaporated to a thickness of 30 nm; the planar substrate 100 is a glass substrate.

Example 19

After the planar substrate 100 is cleaned and dried, 25 nm thick pentacene is sequentially prepared as the first dielectric layer 200, 8 nm thick Ag is used as the metal layer 300, and 25 nm thick pentacene is used as the second dielectric layer. 400, finally forming a multilayer transparent conductive film with a structure of pentacene (25 nm) / Ag (8 nm) / pentacene (25 nm). The planar substrate 100 is a metal aluminum substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by an electron beam evaporation method.

Example 20

After the planar substrate 100 is cleaned and dried, 50 nm thick CuPc is sequentially prepared as the first dielectric layer 200, 8 nm thick Ag is used as the metal layer 300, and 50 nm thick CuPc is used as the second dielectric layer 400, and finally the structure is formed. Multilayer transparent conductive film of CuPc (50 nm) / Ag (8 nm) / CuPc (50 nm). The planar substrate 100 is a metal aluminum substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by an electron beam evaporation method.

Example 21:

The planar substrate 100 is cleaned and dried, and then placed on a carrier of the homogenizer; the planar substrate 100 is a metal aluminum substrate. The dissolved 15 mg/ml organic OXD-7 solution was evenly dropped on a metal aluminum substrate, and spin-coated at 1000 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 75 nm, which was then coated. The metal aluminum substrate of the first dielectric layer 200 is placed in an electron beam evaporation apparatus to evacuate, and when the degree of vacuum reaches 1.2×10 ⁻³ Pascal, 8 nm Ag is evaporated as the metal layer 300, and then the first dielectric layer 200 is provided. The metal aluminum substrate of the metal layer 300 is taken out and placed on the carrier of the homogenizer, and the dissolved 15 mg/ml organic OXD-7 solution is evenly dropped on the metal layer 300, and spin-coated at 1000 rpm. Minutes, a second dielectric layer 400 having a thickness of 75 nm was obtained, and finally a multilayer transparent conductive film having a structure of OXD-7 (75 nm) / Ag (8 nm) / OXD-7 (75 nm) was formed.

Comparative ratio νπ:

The planar substrate 100 is cleaned and dried, and then placed in an electron beam evaporation apparatus to evacuate. When the degree of vacuum reaches 1.2 χ 10 ^-3 Pascals, 8 nm Ag is evaporated; the planar substrate 100 is a metal aluminum substrate.

Example 22 The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a sapphire crystal substrate. The dissolved 10 mg/ml organic OXD-7 solution was evenly dropped on a sapphire crystal substrate, and spin-coated at 1500 rpm for 1 minute to obtain a first dielectric layer 200 having a thickness of 35 nm, which was then coated with The sapphire crystal substrate of the first dielectric layer 200 is placed in a magnetron sputtering coater to evacuate, and a metal thickness of 15 nm is sputtered as a metal layer 300 at a vacuum of 1 Pascal, and then the first dielectric layer 200 is provided. And the sapphire crystal substrate of the metal layer 300 is taken out and placed on the carrier of the homogenizer, and the dissolved 10 mg/ml organic OXD-7 solution is dropped on the metal layer 300, and is rotated at 1500 rpm. After coating for 1 minute, a second dielectric layer 400 having a thickness of 35 nm was obtained, and finally a multilayer transparent conductive film having a structure of OXD-7 (35 nm) / Cu (15 nm) / OXD-7 (35 nm) was formed. Example 23

After the planar substrate 100 is cleaned and dried, 100 nm CuPc is sequentially prepared as the first dielectric layer 200, 15 nm Cu is used as the metal layer 300, and 100 nm CuPc is used as the second dielectric layer 400, and finally the structure is CuPc (100 nm) / Multilayer transparent conductive film of Cu (15 nm) / CuPc (100 nm). The planar substrate 100 is a sapphire crystal substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by a magnetron sputtering method.

Example 24

After the planar substrate 100 is cleaned and dried, 85 nm and pentacene are sequentially prepared as the first dielectric layer 200, 15 nm Cu as the metal layer 300 and 55 nm and pentacene as the second dielectric layer 400, and finally the structure is formed into five. Multilayer transparent conductive film of benzene (85 nm) / Cu (15 nm) / pentacene (55 nm). The planar substrate 100 is a sapphire crystal substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by a magnetron sputtering method.

Example 25:

After the planar substrate 100 is cleaned and dried, 60 nm and pentacene are sequentially prepared as the first dielectric layer. 200, 15 nm Cu as the metal layer 300 and 45 nm CuPc as the second dielectric layer 400, finally forming a multilayer transparent conductive film with a structure of pentacene (60 nm) / Cu (15 nm) / CuPc (45 nm) . The planar substrate 100 is a sapphire crystal substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by a magnetron sputtering method.

Example 26

After the planar substrate 100 is cleaned and dried, 300 nm and pentacene are sequentially prepared as the first dielectric layer 200, 15 nm Cu is used as the metal layer 300, and 25 nm of OXD-7 is used as the second dielectric layer 400, and the structure is finally formed. A multilayer transparent conductive film of pentabenzene (300 nm) / Cu (15 nm) / OXD-7 (25 nm). The planar substrate 100 is a sapphire crystal substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by a magnetron sputtering method.

Example 27

The planar substrate 100 is cleaned and dried to prepare 75 nm of m-MTDATA: F4-TCNQ as the first dielectric layer 200, 15 nm Cu as the metal layer 300 and 75 nm of m-MTDATA: F4-TCNQ as the second The dielectric layer 400 finally forms a multilayer transparent conductive film having a structure of m-MTDATA: F4-TCNQ (75 nm) / Cu (15 nm) / m-MTDATA: F4-TCNQ (75 nm). The mixing ratio of F4-TCNQ is 10%, wherein the planar substrate 100 is a sapphire crystal substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by a magnetron sputtering method.

Example 28

The planar substrate 100 is cleaned and dried to prepare a 150 nm 2T-NATA: F4-TCNQ as the first dielectric layer 200, 15 nm Cu as the metal layer 300 and 150 nm 2T-NATA: F4-TCNQ as the second The dielectric layer 400 finally forms a multilayer transparent conductive film having a structure of 2T-NATA: F4-TCNQC 150 nm)/Cu (15 nm) / 2T-NATA: F4-TCNQ (150 nm). Wherein the mixing ratio of F4-TCNQ For example, 1%, wherein the planar substrate 100 is a sapphire crystal substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by a magnetron sputtering method.

Example 29

The planar substrate 100 is cleaned and dried, and then placed on a homogenizer bracket; the planar substrate 100 is a sapphire crystal substrate. Dissolve 10 mg/ml of P3HT: OXD-7: PVK (P3HT is 1% by mass of the total mass, OXD-7 is 5% of the total mass). The mixed solution is evenly dropped on the sapphire substrate to 1500. Spin/minute speed was spin-coated for 1 minute to obtain a first dielectric layer 200 having a thickness of 30 nm, and then the sapphire crystal substrate coated with the first dielectric layer 200 was placed in a magnetron sputtering coater to evacuate under vacuum. 15 nm Cu was sputtered as a metal layer 300 at 1 Pascal, and then the sapphire crystal substrate with the first dielectric layer 200 and the metal layer 300 was taken out and placed on a homogenizer holder to dissolve 10 mg/ml. P3HT: OXD-7: PVK (the mass of P3HT is 1% of the total mass, and the mass of OXD-7 is 5% of the total mass). The mixed solution is evenly dropped on the metal layer 300 and spin-coated at 1500 rpm. After 1 minute, a second dielectric layer 400 having a thickness of 30 nm was obtained, and finally a multilayer having a structure of P3HT:OXD-7:PVK (30 nm) /Cu(15 nm)/P3HT:OXD-7:PVK (30 nm) was formed. Transparent conductive film.

Comparative ring:

The planar substrate 100 is cleaned and dried, placed in a magnetron sputtering coater, and vacuumed, and 15 nm Cu is sputtered at a vacuum of 1 Pascal; the planar substrate 100 is a sapphire crystal substrate.

Example 30

On the planar substrate 100, 150 nm and pentacene are sequentially prepared as the first dielectric layer 200, 10 nm Ag is used as the metal layer 300, and 35 nm of CuPc is used as the second dielectric layer 400, and finally the structure is pentacene (150 nm) / A multilayer transparent conductive film of Ag (10 nm) / CuPc (35 nm). The planar substrate 100 is a paper substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 was prepared by ion sputtering.

Embodiment 31 - 25 nm pentacene is sequentially prepared as a first dielectric layer 200, 10 nm Ag as a metal layer 300, and 70 nm of OXD-7 as a second dielectric layer 400 on a planar substrate 100, and finally a structure is formed into five Multilayer transparent conductive film of benzene (25 nm) / Ag (10 nm) / OXD-7 (70 nm). The planar substrate 100 is a paper substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by an ion sputtering method.

Example 32 _:

55 nm of m-MTDATA is sequentially prepared on the planar substrate 100: F4-TCNQ is used as the first dielectric layer 200, 10 nm Ag is used as the metal layer 300, and 55 nm of m-MTDATA: F4-TCNQ is used as the second dielectric layer 400, and finally A multilayer transparent conductive film having a structure of m-MTDATA: F4-TCNQ (55 nm) / Ag (10 nm) / m-MTDATA: F4-TCNQ (55 nm) was formed. The mixing ratio of F4-TCNQ is 2%, wherein the planar substrate 100 is a paper substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by an ion sputtering method.

Example 33:

75 nm of 2T-NATA is sequentially prepared on the planar substrate 100: F4-TCNQ is used as the first dielectric layer 200, 10 nm Ag is used as the metal layer 300 and 75 nm of 2T-NATA: F4-TCNQ is used as the second dielectric layer 400, and finally A multilayer transparent conductive film having a structure of 2T-NATA: F4-TCNQ (75 nm) / Ag (10 nm) / 2T-NATA: F4-TCNQ (75 nm) was formed. Wherein the mixing ratio of F4-TCNQ is 2%, wherein the planar substrate 100 is a paper substrate; the first dielectric layer 200 and the second dielectric layer 400 are prepared by a thermal evaporation method, and the metal layer 300 is prepared by an ion sputtering method.

Comparative example IX:

Preparing a metal Ag of 10 nm thickness by ion sputtering on the planar substrate 100; the planar substrate 100 It is a paper substrate.

Example 34 _:

10 nm and pentacene were sequentially prepared on the planar substrate 100 as the first dielectric layer 200, 15 nm Au as the metal layer 300, and 300 nm of OXD-7 as the second dielectric layer 400, and finally the structure was pentacene (10 nm). ) /Au (15 nm) / OXD-7 (300 nm) multilayer transparent conductive film. The planar substrate 100 is a nylon cloth substrate; the first dielectric layer 200, the metal layer 300 and the second dielectric layer 400 are all prepared by a thermal evaporation method.

Example 35

35 nm of m-MTDATA is sequentially prepared on the planar substrate 100: F4-TCNQ is used as the first dielectric layer 200, 15 nm Au is used as the metal layer 300, and 35 nm of m-MTDATA: F4-TCNQ is used as the second dielectric layer 400, and finally A multilayer transparent conductive film having a structure of m-MTDATA: F4-TCNQ (35 nm) / Au (15 nm) / m-MTDATA: F4-TCNQ (35 nm) was formed. The mixing ratio of the F4-TCNQ is 1%, wherein the planar substrate 100 is a nylon cloth substrate; the first dielectric layer 200, the metal layer 300 and the second dielectric layer 400 are all prepared by a thermal evaporation method.

Example 36:

On the planar substrate 100, 120 nm and pentacene are sequentially prepared as the first dielectric layer 200, 15 nm Au as the metal layer 300, and 100 nm of CuPc as the second dielectric layer 400, and finally the structure is pentacene (120 nm) / Multilayer transparent conductive film of Au (15 nm) / CuPc (100 nm). The planar substrate 100 is a nylon cloth substrate; the first dielectric layer 200, the metal layer 300 and the second dielectric layer 400 are all prepared by a thermal evaporation method.

Example 37

55 nm 2T-NATA was prepared sequentially on the planar substrate 100: F4-TCNQ as the first dielectric layer 200, 15 nm Au as the metal layer 300 and 55 nm 2T-NATA: F4-TCNQ as the second medium Layer 400, finally forming a multilayer transparent conductive film of 2T-NATA: F4-TCNQ (55 nm) / Au (15 nm) / 2T-NATA: F4-TCNQ (55 nm). The mixing ratio of the F4-TCNQ is 5%, wherein the planar substrate 100 is a nylon cloth substrate; the first dielectric layer 200, the metal layer 300, and the second dielectric layer 400 are all prepared by a thermal evaporation method.

Comparative example X:

The planar substrate 100 is placed in a thermal evaporation apparatus to evacuate, and when the degree of vacuum reaches 4.0 χ 10· ⁴ Pascal, the metal Au of 15 nm thickness is evaporated; the planar substrate 100 is a nylon cloth substrate.

Example 38 _:

The planar substrate 100 is cleaned and dried to prepare 35 nm of m-MTDATA: F4-TCNQ as the first dielectric layer 200, 15 nm Pt as the metal layer 300 and 35 nm of m-MTDATA: F4-TCNQ as the second The dielectric layer 400 finally forms a multilayer transparent conductive film having a structure of m-MTDATA: F4-TCNQ (35 nm) / Pt (15 nm) / m-MTDATA: F4-TCNQ (35 nm). The mixing ratio of F4-TCNQ is 2%; the planar substrate 100 is a glass substrate; and the first dielectric layer 200, the metal layer 300 and the second dielectric layer 400 are all prepared by a thermal evaporation method.

Example 39

The planar substrate 100 is cleaned and dried to prepare a 35 nm 2T-NATA: F4-TCNQ as the first dielectric layer 200, 15 nm Pt as the metal layer 300 and 35 nm 2T-NATA: F4-TCNQ as the second The dielectric layer 400 finally forms a multilayer transparent conductive film having a structure of 2T-NATA: F4-TCNQ (35 nm) / Pt (15 nm) / 2T-NATA: F4-TCNQ (35 nm). The mixing ratio of F4-TCNQ is 10%; the planar substrate 100 is a glass substrate; and the first dielectric layer 200, the metal layer 300 and the second dielectric layer 400 are all prepared by a thermal evaporation method.

Example 40

After cleaning and drying the planar substrate 100, 30 nm of OXD-7 is prepared in sequence: Benzene: m-MTDATA: F4-TCNQ as the first dielectric layer 200, 15 nm Pt as the metal layer 300 and 30 nm of OXD-7: pentacene: m-MTDATA: F4-TCNQ as the second dielectric layer 400, and finally The formation structure is OXD-7: pentacene: m-MTDATA: F4-TCNQ (30 nm) / Pt (15 nm) / OXD-7: pentacene: m-MTDATA: F4-TCNQ (30 nm) Layer transparent conductive film. Wherein the mass of OXD-7 and pentacles is 1% of the total mass of the mixture, and the mass of F4-TCNQ is 2% of the total mass of the mixture; the planar substrate 100 is a glass substrate; the first dielectric layer 200, the metal layer 300 and The second dielectric layer 400 is prepared by a thermal evaporation method.

Comparative Example XI:

The planar substrate 100 is cleaned and dried, and then placed in a thermal evaporation apparatus to evacuate. When the degree of vacuum reaches 4.0 Χ 10· ⁴ Pascal, the metal Pt of 15 nm thickness is evaporated; the planar substrate 100 is a glass substrate. Example 41:

The structure prepared by using Example 13 as an anode was PVK (35 nm) / Ag (15 nm) / PEDOT: PSS (mass ratio 1:6, 35 nm) / P3HT: PCBM (mass ratio of 1:1, 100 nm) /LiF (1 nm) / Al (100 nm) polymer solar cells. The P3HT and PCBM blends were dissolved in chlorobenzene, and the solution was spin-coated to form a film. Then, the substrate coated with the P3HT:PCBM film was annealed at 160 degrees for 10 minutes using a hot stage, and finally the substrate was placed in a heat. In the evaporation apparatus, when the degree of vacuum reached 4.0 χ 10· ⁴ Pascal, LiF and A1 were sequentially evaporated as a cathode.

Comparative ratio Π:

The structure prepared with ITO as anode is ITO/PEDOT:PSS (mass ratio 1:6, 35 nm) /P3HT:PCBM (mass ratio 1:1,100 nm)/LiF (1 nm)/Al (100 nm) Polymer solar cells. The preparation process of the PEDOT:PSS, P3HT:PCBM, LiF and A1 layers was the same as in Example 41. Table 1 Carrier concentration Hall mobility resistivity sheet resistance

-3

Cm cm V" s" Ω-cm Ω/D Example 1 -8.558x10" 22.08 3.308x10" 4 Example 2 - 7.234x10: 22.21 3.890x10" 4 Example 3 - 6.139x10: 19.67 5.176x10" Example 4 -5.141x10: 20.30 5.989x10"

-4

Example 5 -3.913χ10 ^: 4.666 3.423 10 35

-4

Example 6 -2.101x10: 3.368 8.835x10 19

-4

Example 7 -3.238x10: 3.162 6.105x10 33

-4

Example 8 -4.306x10: 3.574 4.061x10 28

-4

Example 9 -2.125x10: 3.179 9.253x10 25

-4

Implementation - 5.683x10: 10.25 1.073 10 9 Example 11 1.878χ10 ² 8.26 4.028 10" 8 Example 12 - 6.629x10: 13.66 6.902 10" Implementation 13 - 7.838x10: 16.45 4.847 10" 6 Implementation 14 -9.290x10: 17.25 3.901 X10" 6 implementation 15 -4.632x10^ 15.33 8.801x10 9

twenty two

Example 16 -1.025x10 4.019 1.517x10 17 Example 17 -3.848x10: 3.685 4.408x10 22 Example 18 -1.981x10: 3.185 9.905 10 30 Example 19 -9.315x10 8.330 8.055x10 14

-4

Example 20 -4.435x10 8.156 1.728x10 16

-4

Example 21 - 2.706x10: 7.288 !.169x10 20

22 -4

Example 22 -1.154x10 3.209 1.687x10 20

21 -4

Example 23 -4.492x10 3.025 4.599x10 21 Ο寒Λ\卜/s/uooessId sn

Comparative Example IX - 7.620X 10 ²² 15.92 5.152X 10' ⁶ 5 Comparative Example X -3.570X 10 ²² 6.773 2.585χ 10' ⁵ 17 Comparative Example XI -2.833 χ θ θ ²² 7.39 2.985χ 10 ^-5 20

In the above embodiment of the method for producing a highly conductive organic transparent conductive film of the present invention, the second dielectric layer 400 may be the same material as the first dielectric layer 200 or may be a material different from the first dielectric layer 200.

PEDOT: PSS refers to a mixture of PEDOT and PSS; Ρ3ΗΤ: OXD-7 refers to a mixture of Ρ3ΗΤ and OXD-7; 2Τ-ΝΑΤΑ: F4-TCNQ refers to a mixture of 2Τ-ΝΑΤΑ and F4-TCNQ; m-MTDATA: F4-TCNQ refers to a mixture of m-MTDATA and F4-TCNQ; P3HT: PCBM refers to a mixture of P3HT and PCBM; P3HT: OXD-7: PVK refers to a mixture of P3HT, OXD-7 and PVK; OXD-7: and Pentabenzene: m-MTDATA: F4-TCNQ refers to a mixture of OXD-7, pentacene, m-MTDATA and F4-TCNQ. The mixing ratio of F4-TCNQ is 2%, which means that the F4-TCNQ mass accounts for 2% of the total mixture; the F4-TCNQ mixing ratio of 10% means that the F4-TCNQ mass accounts for 10% of the total mixture. The rest will not go into details.

The structures of Examples 1, 2, 3, and 4 are PVK (35 nm) / Ag (12 nm) / P VK (35 nm), PVK (40 nm) / Ag (12 nm) / PVK (40 nm), respectively. PVK (45 nm) / Ag (12 nm) / PVK (45 nm), PVK (55 nm) / Ag (12 nm) / PVK (55 nm). Comparative Example I is a 12 nm metal Ag. It can be seen from Fig. 2 that after adding PVK layers of different thicknesses on both sides of the metal layer of Comparative Example I (Examples 1, 2, 3, 4), the transmittance of metal Ag is obviously improved, and the maximum transmission is obtained. The rate is 89%, and the transmission spectrum of the multilayer film can be adjusted by changing the thickness of the PVK layer.

The structure of Example 5 was PVK (40 nm) / Au (8 nm) / PVK (40 nm), and Comparative Example II was 8 nm metal Au. It can be seen from FIG. 3 that the average visible light transmittance of Example 5 exceeds 75%. Significantly higher than Comparative Example II.

Example 41 and Comparative Example The open circuit voltage, short circuit current density, fill factor, and energy conversion efficiency of ΧΠ were 0.60 and 0.62 volts, 8.23 and 8.88 mA/cm 2 , 0.60 and 0.59, 2.95%, and 3.23%, respectively. It can be seen from Fig. 4 that the performance of the polymer solar cell prepared by using the organic transparent conductive film as the anode is similar to that of the polymer solar cell prepared by using the conventional ITO electrode as the anode, indicating that such a novel transparent conductive film can be substituted. ITO is used in the field of organic optoelectronics, which will help to further reduce the cost of optoelectronic devices.

Table 1 shows Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 , 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40 and Comparative Examples I, II, III, IV, V, VI , VII, ring, IX, X, XI carrier concentration, Hall mobility, resistivity and sheet resistance parameters. It can be seen from Table 1 that a dielectric/metal/dielectric multilayer structure prepared by using different organic dielectric layers and metal layers can obtain an n-type or p-type transparent conductive film, and the mobility of the transparent conductive film is higher than that of a conventional organic semiconductor. The mobility of the material (l(T ³ -l (T ⁷ cm ^{2 is} increased by 3-8 orders of magnitude and a sheet resistance of 4-35 Ω/□ can be achieved.

Claims

Claim

Step i: preparing a first dielectric layer on a rigid or flexible planar substrate;

Step i i, preparing a metal layer on the first dielectric layer;

Step i i i, preparing a second dielectric layer on the metal layer;

2. The preparation method according to claim 1, wherein the organic semiconductor material comprises an organic small molecule semiconductor material and a polymer semiconductor material.

The method according to claim 2, wherein when the first dielectric layer and the second dielectric layer are a mixture of two organic semiconductor materials, the mass mixing ratio of the two materials is 1:99. -1 : 4.

The preparation method according to claim 2, wherein the first dielectric layer and the second dielectric layer are mixed with three or more organic semiconductor materials, wherein each of the materials has at least the mass 1% of the total mass of the mixture.

The preparation method according to any one of claims 1 to 4, wherein the first dielectric layer and the second dielectric layer have a thickness of 10-300 nm, respectively.

The preparation method according to any one of claims 1 to 4, wherein the materials of the first dielectric layer and the second dielectric layer are respectively any one of the following materials or mixtures: polyvinyl ruthenium a mixture of azole (PVK), OXD-7, pentacene, copper phthalocyanine (CuPc), poly(3 hexylthiophene) (P3HT) and OXD-7, a mixture of PEDOT and PSS, a mixture of 2T-NATA and F4-TCNQ, a mixture of m-MTDATA and F4-TCNQ, a mixture of P3HT: OXD-7: PVK or a mixture of pentacene: OXD-7: m-MTDATA: F4-TCNQ, and the like.

The preparation method according to any one of claims 1 to 4, wherein when the first dielectric layer and the second dielectric layer are prepared by spin coating, the spin coating speed is 500-3000 rpm/ In minutes, the spin time is 1-2 minutes.

The preparation method according to any one of claims 1 to 4, wherein the metal layer material is Ag, Au, Pt or Cu or the like; and the metal layer has a thickness of 8 to 30 nm.

The preparation method according to any one of claims 1 to 4, wherein the metal layer is produced by electron beam evaporation, thermal evaporation, magnetron sputtering or ion sputtering.

The preparation method according to any one of claims 1 to 4, wherein in the step i, the rigid planar substrate is glass, quartz, metal, inorganic crystal or semiconductor; the flexible planar substrate is plastic , paper or cloth.