WO2018028244A1

WO2018028244A1 - Transparent conductive film, preparation method therefor and application thereof

Info

Publication number: WO2018028244A1
Application number: PCT/CN2017/081648
Authority: WO
Inventors: 潘锋; 梁军; 杨晓杨; 林海; 吴忠振; 刘屹东
Original assignee: 北京大学深圳研究生院
Priority date: 2015-09-18
Filing date: 2017-04-24
Publication date: 2018-02-15
Also published as: CN106191775A

Abstract

Disclosed are a transparent, conductive and doped titanium dioxide film, a preparation method therefor, and an application thereof. The transparent conductive film of the present application is a doped titanium dioxide film, wherein "doped" is ruthenium-doped as well as niobium- and/or tantalum-doped. According to the transparent conductive film of the present application, a titanium dioxide is doped with ruthenium, and is also doped with one or both of niobium and tantalum, so that the prepared doped titanium dioxide film has excellent electrical conductivity, good temperature resistance, and high light transmittance. Moreover, the transparent conductive film of the present application has low raw material costs and rich resources, and the preparation method therefor is also simple and easy to operate, thereby meeting needs of large-scale batch production, and laying a foundation for spread, application and research of the transparent conductive film.

Description

Transparent conductive film and preparation method and application thereof

Technical field

The present application relates to the field of transparent conductive films, and in particular to a transparent conductive film and a preparation method and application thereof.

Background technique

With the rapid development of the flexible display industry worldwide, the demand for large-area transparent conductive oxide (abbreviated TCO) glass substrates will continue to grow rapidly for a long time. According to preliminary estimates, by 2020, the demand for TCO glass substrates worldwide will exceed 1.2 billion square meters. The transparent conductive film widely used in the industry mainly includes indium tin oxide (abbreviated as ITO), zinc aluminum oxide (abbreviated as AZO) and fluorine-doped tin oxide (abbreviated FTO). Among them, ITO is greatly limited in its application due to the large use of expensive indium materials. The photoelectric performance of FTO and AZO systems is close to that of ITO, which is partially applied in flat panel displays. However, the high temperature process needs to be introduced in the preparation process of FTO and AZO, and the production conditions are relatively high, which limits the wide application of FTO and AZO. .

In order to further reduce the cost, avoid the use of rare metal indium, and not lower the performance of the conductive film, and make the TCO more competitive in production, it is necessary to solve the problem of the material of the transparent conductive film as a key problem. Titanium dioxide-based film has been widely used in photocatalysis applications because of its excellent optoelectronic properties, low cost and abundant resources. However, when it is used as a conductive film, its conductivity and light transmittance are poor, and good results cannot be obtained. .

Summary of the invention

The object of the present application is to provide an improved new transparent conductive film and a preparation method and application thereof.

This application uses the following technical solutions:

One aspect of the present application discloses a transparent conductive film that is a doped titanium dioxide film in which doping is doped with germanium and germanium and/or germanium doping.

It should be noted that the key of the present application is to creatively dope doping in titanium dioxide, at the same time, doping one or both of lanthanum and cerium into carbon dioxide; making the prepared doped titanium dioxide film When used as a transparent conductive film, it has good electrical conductivity and light transmittance, and its performance is comparable to that of current mainstream ITO, FTO and AZO. However, the doping of titanium dioxide has much lower raw material cost and production cost, and its preparation method is simple and easy to operate. Can meet the needs of large-scale mass production. The transparent conductive film of the present application has a conductivity improvement of more than two times and a light transmittance of 10%; a high temperature resistance in a reducing atmosphere and a plasma atmosphere, and the stability is much higher than that of ITO and AZO; F The source is a toxic substance; and it has a high transmittance in the ultraviolet-visible-infrared spectrum, and is particularly suitable for use in thin film solar cell devices, flat display devices, touch screen devices, and infrared devices.

It will be appreciated that the key to the present application is the inventive discovery that doping yttrium, and one or both of tantalum and niobium in a titanium dioxide film can provide a transparent conductive film with good properties; as for tantalum, niobium and/or tantalum The specific doping amount may be determined according to different production requirements or product requirements, and is not specifically limited herein. However, in the preferred embodiment of the present application, in order to secure a more stable and good transparent conductive film, the doping amount of ruthenium, osmium and/or iridium is particularly limited, and a detailed scheme will be described below.

Preferably, the amount of antimony doping is 0.1-5% by weight, the amount of antimony doping is 0.1-20% of the total weight, and the amount of antimony doping is 0.1-20% of the total weight.

Preferably, the crystal phase of the titanium dioxide is an anatase phase.

The other side of the application also discloses the use of the transparent conductive film of the present application in a display screen, a touch screen, a photovoltaic device or an optoelectronic device.

It can be understood that the transparent conductive film of the present application, the raw materials of titanium dioxide, lanthanum, cerium, lanthanum, are all cheap and resource-rich raw materials, and its performance is also comparable to the current mainstream ITO, FTO and AZO, so there is no cost concern. In this case, applications for ITO, FTO and AZO can be replaced; especially in displays, touch screens or optoelectronic devices.

The other side of the application also discloses a transparent conductive glass comprising a substrate and a conductive film, the conductive film of which is the transparent conductive film of the present application, and the substrate is at least one of glass, quartz, sapphire and organic film.

Another aspect of the present application also discloses a composite electrode comprising the transparent conductive film of the present application.

The other side of the application also discloses a preparation method of the transparent conductive film of the present application, which comprises preparing a yttrium and/or yttrium-doped titanium dioxide film by magnetron sputtering, and then performing a ruthenium and/or yttrium-doped titanium dioxide film.钌 compound treatment; magnetron sputtering method comprises: mixing lanthanum source powder and/or lanthanum source powder with titanium dioxide powder in a stoichiometric ratio, grinding uniformly, and then calcining at high temperature to form doped titania target, using magnetron sputtering The ruthenium and/or ruthenium-doped titanium dioxide film is prepared; the ruthenium compound treatment comprises: immersing the ruthenium and/or ruthenium-doped titanium dioxide film in the ruthenium compound solution, reacting at 10 to 150 ° C for 10 to 120 minutes, and then argon and/or The cerium-doped titanium dioxide film is placed in a vacuum or an inert atmosphere or a reducing atmosphere, and is kept at 100 to 650 ° C for 0 to 10 hours, and cooled to room temperature to obtain a cerium doped film, and a cerium and/or cerium doped titanium dioxide film.

It should be noted that the magnetron sputtering method of the present application is carried out under vacuum, so it is also referred to as vacuum preparation of a doped titanium dioxide film. Among them, the preparation of the target can be referred to the preparation of a general magnetron sputtering target, which is not described here; as for the amount of the source powder, the source powder and the titanium dioxide powder in the target, according to different production requirements and products. Demand regulation, not to mention here. "And/or" means that it may be doped with antimony doping and antimony doping, or it may be doped or antimony doped. Specific strip of magnetron sputtering The magnetron sputtering method can also be referred to in accordance with the thickness of the desired tantalum and/or niobium doped titanium dioxide film. In the preferred embodiment of the present application, the magnetron sputtering conditions are specifically limited. In addition, the concentration of the ruthenium compound solution, as well as the specific treatment time and temperature, etc., can be adjusted according to the amount of ruthenium doping required; it can be understood that if the amount of ruthenium required to be doped is larger, under the condition that the chemical dose is allowed, The use of a higher concentration of ruthenium compound, the treatment time is longer, the temperature is higher, and vice versa; it is not specifically limited herein.

Preferably, the cerium compound is at least one of a halogen cerium, a cerium oxide, a cerium salt, and a cerium organic compound.

Preferably, the cerium source powder is nano cerium powder and/or tantalum pentoxide; the cerium source powder is nano cerium powder and/or tantalum pentoxide.

Preferably, the specific conditions for the magnetron sputtering to form the tantalum and/or niobium doped titanium dioxide film are: sputtering chamber pressure is 0.1-10 Pa, sputtering chamber atmosphere is argon or nitrogen or argon hydrogen mixed gas, substrate The glass, quartz plate, sapphire or organic substrate has a substrate temperature of 10 to 500 ° C, a sputtering power of 0.01 to 10 W/cm ² , a deposition rate of 0.1 to 500 nm/min, and a sputtering time of 0.01 to 5 hours.

Another aspect of the present application also discloses another method of preparing the transparent conductive film of the present application, comprising dispersing a source of germanium and/or germanium together with a source of germanium and a source of titanium in a stoichiometric ratio in a solvent, in air or The thermal reaction is carried out under an inert atmosphere, the reaction product is coated on a substrate, and the solvent is dried to obtain a ruthenium doping, and a ruthenium and/or ruthenium-doped titanium oxide film.

It should be noted that, in one implementation of the present application, the reaction product is further diluted in advance according to specific test requirements before the reaction product is applied to the substrate. In another implementation of the present application, the reaction product solution is further concentrated before being applied to the substrate, and then placed in a reaction vessel at a high temperature and high pressure treatment, and then centrifuged to obtain a sinking bottom, using a solvent pair. The precipitate was dispersed and applied as a coating liquid to the substrate. That is to say, the steps of performing various treatments on the reaction product solution may be included before the reaction product is applied to the substrate according to different production conditions or specific production conditions, and are not specifically limited herein.

Another aspect of the present application also discloses a further preparation method of the transparent conductive film of the present application, which comprises dispersing a source of germanium and/or germanium with a source of titanium in a stoichiometric ratio to a solvent under air or an inert atmosphere. Performing a thermal reaction, coating the reaction product on a substrate, drying the solvent to obtain a ruthenium and/or ruthenium-doped titanium dioxide film; and immersing the ruthenium and/or ruthenium-doped titanium dioxide film in the ruthenium compound solution at 10 to 150 The reaction is carried out at °C for 10 to 120 minutes, and then the ruthenium and/or ruthenium-doped titanium dioxide film is placed in a vacuum or an inert atmosphere or a reducing atmosphere, and is kept at 100 to 650 ° C for 0 to 10 hours, and cooled to room temperature to obtain ruthenium doping, and ruthenium. And/or antimony doped, titanium dioxide film.

It should be noted that the difference between the above two preparation methods is whether or not the germanium source is added to the reaction liquid, and if the germanium source is added, the germanium doping and the germanium and/or germanium doping dioxide can be directly prepared. Titanium film; if no lanthanum source is added, the prepared ruthenium and/or ruthenium-doped titanium dioxide film needs to be treated with ruthenium compound.

Preferably, the thermal reaction is carried out at a temperature of from 30 to 300 ° C for from 0.1 to 6 hours.

Preferably, the cerium source is at least one of cerium chloride, cerium ethoxide, nano cerium powder and antimony pentoxide; the cerium source is cerium chloride, cerium ethoxide, nano cerium powder, cerium pentoxide and methanol cerium. At least one; the titanium source is at least one of n-butyl titanate, isopropyl titanate, and tetraethyl titanate.

Preferably, the solvent is at least one of distilled water, ethanol, n-butanol, acetonitrile, methanol, 2-methoxyethanol, isopropanol, ethylene glycol, N,N-dimethylformamide, and tetrahydrofuran.

The beneficial effects of the present application are:

The transparent conductive film of the present application is doped with antimony in titanium dioxide and simultaneously doped with one or two of cerium and lanthanum, so that the prepared doped titanium dioxide film has excellent electrical conductivity, good temperature resistance and high light transmittance; Moreover, the transparent conductive film of the present application has low raw material cost and abundant resources, and the preparation method thereof is simple and easy to operate, and can meet the demand of large-scale mass production, and lays a foundation for popularization and application and research of the transparent conductive film.

DRAWINGS

1 is an X-ray diffraction chart of a transparent conductive film in an embodiment of the present application;

2 is an X-ray diffraction diagram of a transparent conductive film in another embodiment of the present application;

3 is a transmission spectrum of a transparent conductive film in another embodiment of the present application, wherein the small image is a physical map;

4 is an X-ray diffraction diagram of a transparent conductive film in another embodiment of the present application;

5 is a comparison diagram of ultraviolet-visible-infrared transmission spectra of a transparent conductive film and ITO and FTO in another embodiment of the present application;

6 is a J-V curve and photoelectric conversion efficiency of a transparent conductive film used as an electrode in an organic thin film solar cell according to another embodiment of the present application;

7 is a J-V curve and photoelectric conversion efficiency of a transparent conductive film used as an electrode in a cadmium telluride thin film solar cell according to another embodiment of the present application.

detailed description

The present application is further described in detail below by way of specific embodiments. The following examples are only intended to further illustrate the present application and are not to be construed as limiting the invention.

Embodiment 1

In the transparent conductive film of this example, an antimony-doped titanium dioxide film is prepared by magnetron sputtering, and then treated with barium chloride to obtain an antimony doped and antimony doped titanium dioxide film. details as follows:

(1) The titanium dioxide powder and the tantalum pentoxide powder are used as the main raw materials, the purity is 4N to 5N, and the molar ratio of Ti:Nb is 9:1, and after mixing, it is ground and uniformly mixed. Then, it was pre-fired at 820 ° C for 3 h in a high-temperature silicon molybdenum furnace; after completion, 5 mL of a polymerization agent polyvinyl alcohol was added, and a circular target having a thickness of 4.5 mm and a diameter of 5 cm was pressed by a powder tableting machine, and then placed in a high-temperature silicon. In the molybdenum furnace, it was sintered at 5 ° C / min to 1350 ° C for 5 h. After cooling, a 0.5 mm thick copper backing was fixed to obtain a cerium-doped titanium dioxide target. (2) The obtained cerium-doped titanium dioxide target was prepared by magnetron sputtering to prepare a cerium-doped titanium dioxide film, wherein the sputtering chamber pressure was 0.3 Pa, the sputtering chamber atmosphere was argon gas, and the substrate was soda-lime-silica glass. The substrate temperature was 25 ° C, the sputtering power was 0.5 W/cm ² , the deposition rate was 10 nm/min, and the sputtering time was 1 h. A tantalum-doped titanium dioxide film having a thickness of 600 nm was prepared. (3) lanthanum-doped titanium dioxide film treated with lanthanum chloride, immersed lanthanum-doped titanium dioxide film in lanthanum chloride solution at 50 ° C for 10 min, then taken out in an inert atmosphere heated to 450 ° C, kept for 30 min, cooled to room temperature A tantalum-doped and antimony-doped titanium dioxide film, that is, a transparent conductive film of this example, is obtained.

The transparent conductive film prepared in this example was examined by X-ray diffraction. The results are shown in Fig. 1. In the transparent conductive film prepared in this example, the crystal form is mainly anatase. The doped titanium dioxide with good crystallinity has good preference and large crystal grains. The carrier mobility of more than 10 cm ² /Vs was obtained by the Hall tester, and the carrier concentration was close to 10 ²⁰ cm ^-3 . It can be seen that the transparent conductive film prepared in this example has good conductivity. In addition, a transmittance of more than 80% was obtained by a transmission spectrometer test.

The above test results show that the transparent conductive film of this example can achieve the performance indexes of mature products such as ITO, AZO and FTO. However, the transparent conductive film of the present example is a ruthenium and osmium doped titanium dioxide film, which has low raw material cost, abundant resources, and has greater cost and resource advantages, and the preparation method of the present example is simple and easy to operate, and the production cost is low. Suitable for large-scale production.

Embodiment 2

(1) The ruthenium-doped titania target was prepared in the same manner as in Example 1 using a tantalum pentoxide having a purity of 4N to 5N and a Ti:Ta molar ratio of 19:1. (2) Then the erbium-doped TiO2 film was prepared by magnetron sputtering on the yttrium-doped TiO2 target. The magnetron sputtering conditions were as follows: the sputtering chamber pressure was 1.0 Pa, the sputtering chamber atmosphere was argon, and the substrate was A soda-lime-silica glass having a substrate temperature of 50 ° C, a sputtering power of 0.3 W/cm ² , a deposition rate of 8 nm/min, and a sputtering time of 1 h was prepared to have a thickness of 400 nm. (3) The obtained cerium-doped titanium dioxide film is treated with cerium chloride, and the cerium-doped titanium dioxide film is immersed in a cerium chloride solution at 60 ° C for 10 minutes, then taken out and heated to 500 ° C under an inert atmosphere, kept for 30 minutes, and cooled. At room temperature, an antimony doped and antimony doped titanium dioxide film, that is, a transparent conductive film of this example, was obtained.

The transparent conductive film prepared in this example was examined by the same method as in Example 1. The results are shown in Fig. 2, which shows that the crystal form is mainly anatase by X-ray diffraction. The Hall tester obtains a carrier mobility of more than 10 cm ² /Vs, a carrier concentration of approximately 10 ²⁰ cm ^-3 , and a sheet resistance of 10 to 100 Ω/sq, and the transparent conductive film has good conductivity. In addition, the light transmittance in the visible light range is as high as 80%, as shown in FIG. 3, and FIG. 3 respectively shows the light transmittance of the transparent conductive film which is annealed and not annealed, and is not annealed after being immersed in cesium chloride. It is not heated and heated at 500 ° C for 30 min in an inert atmosphere; in the figure, curve 1 is the transmittance of the annealed transparent conductive film, and curve 2 is the transmittance of the transparent conductive film which has not been annealed, and it can be seen that after annealing The transparent conductive film of this example has a markedly improved light transmittance.

It can be seen that the transparent conductive film of this example has the same performance as the transparent conductive film of the first embodiment, and can reach a mature product on the market. Moreover, the transparent conductive film of the present example is a ruthenium and osmium doped titanium dioxide film, which has low raw material cost, abundant resources, greater cost and resource advantages, simple and easy to operate, low production cost, and is more suitable for large Scale production.

Embodiment 3

In the transparent conductive film of this example, yttrium and lanthanum-doped titanium dioxide films were prepared by magnetron sputtering, and then lanthanum chloride treatment was carried out to obtain yttrium-doped, ytterbium-doped and ytterbium-doped TiO 2 films. details as follows:

(1) The tantalum source of this example is tantalum pentoxide, the tantalum source is tantalum pentoxide, the purity is 4N to 5N, and the molar ratio of Ti:Nb:Ta is 18:1:1, which is the same as that of the first embodiment. The method of preparing ruthenium and osmium doped titania targets. (2) The yttrium-doped titania target was then subjected to magnetron sputtering to prepare a yttrium-doped titanium dioxide film. The magnetron sputtering conditions were as follows: the sputtering chamber pressure was 1.0 Pa, and the sputtering chamber atmosphere was argon. The bottom is soda-lime-silica glass, the substrate temperature is 200 ° C, the sputtering power is 0.3 W/cm 2 , the deposition rate is 8 nm/min, and the sputtering time is 1 h, and a ruthenium and osmium-doped titanium dioxide film having a thickness of 400 nm is prepared. (3) The obtained ruthenium and osmium-doped titanium dioxide film is treated with ruthenium chloride, and the ruthenium-doped titanium dioxide film is immersed in a ruthenium chloride solution at 40 ° C for 60 minutes, and then taken out and heated to 500 ° C under an inert atmosphere for 30 minutes. After cooling to room temperature, a ruthenium-doped, ruthenium and osmium-doped titanium dioxide film, that is, a transparent conductive film of this example, was obtained.

The transparent conductive film prepared in this example was examined by the same method as in Example 1. The results showed that the crystal form was mainly anatase by X-ray diffraction. The Hall tester obtained a carrier mobility of more than 10 cm ² /Vs, a carrier concentration of approximately 10 ²⁰ cm ^-3 , and a sheet resistance of 100 to 300 Ω/sq, and the transparent conductive film was excellent in electrical conductivity. In addition, the light transmittance in the visible light range is as high as 80%.

It can be seen that the transparent conductive film of this example has the same performance as the transparent conductive film of the first embodiment, and can reach a mature product on the market. Moreover, the transparent conductive film of the present example is a titanium dioxide film doped with lanthanum, cerium and lanthanum. The raw material is low in cost, rich in resources, has greater cost and resource advantages, and the preparation method is simple and easy to operate, and the production cost is low, and is more suitable. For mass production.

Embodiment 4

In the transparent conductive film of this example, a ruthenium-doped titanium dioxide film is prepared by a solution coating method, and then subjected to ruthenium chloride treatment to obtain a ruthenium-doped and ruthenium-doped titanium oxide film. details as follows:

(1) Preparation of coating liquid: the pure reagent is analyzed by using n-butyl titanate as the source of titanium, and antimony pentachloride is used as the source of niobium. According to the molar ratio of titanium source and niobium source: 90:10, that is, tetrabutyl titanate 1.531g, 0.135g of antimony pentachloride, added to the ethanol solution, stirred evenly, heated at 80 ° C in air atmosphere, stirred for 1h, prepared a colored gel, concentrated on the gel, and transferred to water heat In the autoclave, after treatment at 210 ° C for 4 h, the product powder was centrifuged, and the product powder was redispersed into ethanol to obtain a coating liquid B. (2) Film formation: Coating liquid B was blade-coated on a white glass substrate, and then the solvent was dried at 120 ° C to obtain a ruthenium-doped titanium oxide film. (3) Barium chloride treatment: the surface of the antimony-doped titanium dioxide film of step (2) is cleaned. In this example, the surface is cleaned by UV irradiation for 30 min, then immersed in a barium chloride solution at 70 ° C for 15 min, and taken out after soaking. The film was heated to 450 ° C under a nitrogen atmosphere, kept for 0.5 h, and cooled to room temperature to obtain an 800 nm thick yttrium-doped and ytterbium-doped titanium oxide film, that is, the transparent conductive film of this example.

The conductivity and light transmittance of the transparent conductive film of this example were tested. The results show that the transparent conductive film of this example has a transmittance of 75% in the visible light range, a sheet resistance of 100 to 500 Ω/sq, and X-ray diffraction test. The crystal form is mainly anatase, as shown in Figure 4. It can be seen that the transparent conductive film of this example also has good photoelectric properties.

Embodiment 5

(1) Preparation of coating liquid: the pure reagent of isopropyl titanate is used as the source of titanium, and the antimony pentachloride is used as the source of lanthanum. According to the molar ratio of titanium source and lanthanum source: 95:5, that is, tetrabutyl titanate 1.35g, bismuth pentachloride is 0.068g, added to the ethanol solution, stirred evenly, heated at 80 ° C in air atmosphere, stirred for 1h, to prepare a colored gel, diluted with ethanol to obtain a coating Liquid coating. (2) Film formation: The coating liquid was spin-coated on a white glass substrate, spin-coated at 1.5 k rpm, applied 5 times, and then the solvent was dried at 120 ° C to obtain a ruthenium-doped titanium oxide film. (3) Barium chloride treatment: the cerium-doped titanium dioxide film of step (2) Surface cleaning, this example uses UV irradiation for 30min for surface cleaning, then immersed in barium chloride solution at 70 ° C for 15min, remove the soaked film, heated to 450 ° C under nitrogen atmosphere, heat preservation 0.5h, cooling to room temperature That is, a 500 nm thick antimony doped and antimony doped titanium dioxide film, that is, a transparent conductive film of this example is obtained.

The conductivity and light transmittance of the transparent conductive film of this example were tested. The results show that the transparent conductive film of this example has a transmittance of 75% in the visible light range, a sheet resistance of 100 to 500 Ω/sq, and X-ray diffraction test. The crystal form is mainly anatase. It can be seen that the transparent conductive film of this example also has good photoelectric properties.

Embodiment 6

In the transparent conductive film of this example, a tantalum and niobium doped titanium dioxide film was prepared by a solution coating method. details as follows:

(1) Preparation of coating liquid: the pure reagent is analyzed by tetraethyl titanate as the source of titanium, antimony pentachloride is used as the source of antimony, and barium chloride is used as the source of antimony. According to the source of titanium: antimony pentachloride and antimony chloride The molar ratio of 96:4, that is, tetraethyl titanate is 1.095g, ruthenium pentachloride is 0.041g, ruthenium chloride is 0.010g, added to the ethanol solution, stirred uniformly, heated at 80 ° C under argon atmosphere, stirred After 1 h, the temperature was further raised to 120 ° C, and stirred for 1 h to prepare a dark brown solution A, which was diluted with ethanol to prepare a coating liquid. (2) Film formation: The coating solution was spin-coated on a white glass substrate, spin-coated at 1.5 k rpm, coated twice, then dried at 120 ° C, and cooled to room temperature to obtain a 450 nm thick bismuth blend. The hetero and antimony doped titanium dioxide film, that is, the transparent conductive film of this example.

Example 7

In the transparent conductive film of this example, a ruthenium and osmium-doped titanium dioxide film is prepared by a solution coating method, and then subjected to ruthenium chloride treatment to obtain a ruthenium-doped, ruthenium- and osmium-doped titanium oxide film. details as follows:

(1) Preparation of coating liquid: the pure reagent is analyzed by tetraethyl titanate as the source of titanium, antimony pentachloride is used as the source of antimony, and barium chloride is used as the source of antimony. According to the source of titanium: antimony pentachloride and antimony chloride The molar ratio of 97:3, that is, tetraethyl titanate is g, ruthenium pentachloride is 0.027 g, and ruthenium chloride is 0.018 g, added to an ethanol solution, stirred uniformly, heated at 80 ° C in an air atmosphere, and stirred for 1 h. The mixture was further heated to 120 ° C and stirred for 1 hour to prepare a dark brown solution A, which was diluted to prepare a coating liquid. (2) Film formation: spraying the coating liquid to white On the glass substrate, the spray was sprayed for 20 min, the temperature of the substrate was maintained at 120 ° C, and the tantalum and niobium doped titanium dioxide film was directly obtained after the spray coating was completed. (3) Barium chloride treatment: surface cleaning of the cerium and lanthanum-doped titanium dioxide film of step (2), this example is surface-cleaned by UV irradiation for 5 min, and then immersed in a barium chloride solution at 70 ° C for 15 min, and taken out. The soaked film was heated to 350 ° C under a nitrogen atmosphere, kept for 1 h, and cooled to room temperature to obtain a 600 nm thick antimony doped, lanthanum and cerium doped titanium dioxide film, that is, the transparent conductive film of this example.

Similarly, the transparent conductive film of this example was tested for conductivity and light transmittance, and the results showed that the transparent conductive film of this example had a transmittance of 75% in the visible light range, a sheet resistance of 100 to 500 Ω/sq, and X. The crystal form of the diffraction test is mainly anatase. It can be seen that the transparent conductive film of this example also has good photoelectric properties.

Example eight

In this example, the yttrium-doped titanium dioxide film was prepared by magnetron sputtering in the same manner as in the first embodiment, and then subjected to lanthanum chloride treatment to obtain yttrium-doped and yttrium-doped TiO 2 films. The transparent conductive film prepared in this example was tested. The results showed that the crystal form was mainly anatase by X-ray diffraction. The Hall tester has a carrier mobility of 3-10 cm ² /Vs, a carrier concentration of 10 ²¹ cm ^-3 , and a sheet resistance of 5 to 20 Ω/sq, and the transparent conductive film has good conductivity.

In addition, the transparent conductive film prepared in this example was subjected to ultraviolet-visible-infrared transmittance test, and the conventional ITO and FTO were used for comparison test. The results show that the transparent conductive film of this example has a transmittance of 70-80% in the ultraviolet-visible-infrared range, as shown in Fig. 5, especially at a transmittance of 1200 nm or more, while the conventional ITO or FTO is 1200 nm. The light transmittance of the light wave is significantly reduced. It can be seen that the transparent conductive film of this example has excellent performance in the electrode application of the infrared device. In FIG. 5, curve 1 is a light transmittance test curve of the transparent conductive film of the present example, curve 2 is a test curve of ITO, and curve 3 is a test curve of FTO.

Example nine

In the transparent conductive film of the organic solar cell of the present example, the yttrium-doped titanium dioxide film was prepared by magnetron sputtering in the same manner as in the first embodiment, and then subjected to lanthanum chloride treatment to obtain an yttrium-doped and yttrium-doped TiO 2 film. . The transparent conductive film prepared in this example was tested. The results showed that the crystal form was mainly anatase by X-ray diffraction. The Hall tester has a carrier mobility of 3-10 cm ² /Vs, a carrier concentration of 10 ²¹ cm ^-3 , and a sheet resistance of 10 to 20 Ω/sq, and the transparent conductive film has good conductivity. In addition, the light transmittance in the visible light range is as high as 80%. After the conductive film was washed, ZnO (about 30 nm), P3HT: PCBM (about 200 nm), MoO3 (about 5-10 nm), and Ag (about 150 nm) were sequentially deposited. details as follows:

(1) The titanium dioxide powder and the tantalum pentoxide powder are used as the main raw materials, the purity is 4N to 5N, and the molar ratio of Ti:Nb is 19:1, and after mixing, it is ground and uniformly mixed. Then, it was pre-fired at 820 ° C for 3 h in a high-temperature silicon molybdenum furnace; after completion, 5 mL of a polymerization agent polyvinyl alcohol was added, and a circular target having a thickness of 4.5 mm and a diameter of 5 cm was pressed by a powder tableting machine, and then placed in a high-temperature silicon. In the molybdenum furnace, it was sintered at 5 ° C / min to 1350 ° C for 5 h. After cooling, a 0.5 mm thick copper backing was fixed to obtain a cerium-doped titanium dioxide target. (2) The obtained cerium-doped titanium dioxide target was prepared by magnetron sputtering to prepare a cerium-doped titanium dioxide film, wherein the sputtering chamber pressure was 0.3 Pa, the sputtering chamber atmosphere was argon gas, and the substrate was soda-lime-silica glass. A ruthenium-doped titanium dioxide film having a thickness of 360 nm was prepared at a substrate temperature of 25 ° C, a sputtering power of 0.5 W/cm ² , a deposition rate of 4 nm/min, and a sputtering time of 1.5 h. (3) lanthanum-doped titanium dioxide film treated with lanthanum chloride, immersed lanthanum-doped titanium dioxide film in lanthanum chloride solution at 50 ° C for 10 min, then taken out in an inert atmosphere heated to 450 ° C, kept for 30 min, cooled to room temperature A tantalum-doped and antimony-doped titanium dioxide film, that is, a transparent conductive film of this example, is obtained. (4) The obtained conductive film was ultrasonically washed with detergent, distilled water, acetone, and isopropyl alcohol, and then dried at 80 °C. (5) After the surface of the conductive film is treated by UV/ozone, spin-coated ZnO precursor solution, treated at 200 ° C for 1 h, then spin-coated P3HT: PCBM (1:1), after drying the solvent at 150 ° C, evaporation 5 nm MoO ₃ and finally 150 nm Ag were evaporated to obtain an organic solar cell in this example.

The obtained solar cell was tested in an AM 1.5G environment (100 mW cm ^-2 ), and the results are shown in Fig. 6. In the figure, curve 1 is a test curve using the transparent conductive film of the present application, and curve 2 is a test using ITO. curve. The open circuit voltage of the obtained battery was 0.557 V, the short circuit current was 8.21 mA/cm ² , the filling factor was 49.73%, and the photoelectric conversion efficiency was 2.27%. The comparative sample was made of ITO as the conductive film, and the open circuit voltage of the battery was 0.572 V, the short circuit current was 6.42 mA/cm ² , the filling factor was 63.89%, and the photoelectric conversion efficiency was 2.35%. It can be seen that the transparent conductive film of this example has excellent performance in optoelectronic device applications.

Example ten

In the transparent conductive film of the cadmium telluride thin film solar cell, the yttrium-doped titanium dioxide film was prepared by magnetron sputtering in the same manner as in the first embodiment, and then lanthanum chloride was treated to obtain yttrium doping and ytterbium doping. Titanium dioxide film. The transparent conductive film prepared in this example was tested. The results showed that the crystal form was mainly anatase by X-ray diffraction. The Hall tester has a carrier mobility of 3-10 cm ² /Vs, a carrier concentration of 10 ²¹ cm ^-3 , and a sheet resistance of 10 to 20 Ω/sq, and the transparent conductive film has good conductivity. In addition, the light transmittance in the visible light range is as high as 80%. After the conductive film was washed, CdS (about 150 nm), CdTe (4-5 μm), Cu (about 1-5 nm), and Au (about 80 nm) were sequentially deposited. details as follows:

(1) The titanium dioxide powder and the tantalum pentoxide powder are used as the main raw materials, the purity is 4N to 5N, and the molar ratio of Ti:Ta is 19:1, and after mixing, it is ground and uniformly mixed. Then, it was pre-fired at 820 ° C for 3 h in a high-temperature silicon molybdenum furnace; after completion, 5 mL of a polymerization agent polyvinyl alcohol was added, and a circular target having a thickness of 4.5 mm and a diameter of 5 cm was pressed by a powder tableting machine, and then placed in a high-temperature silicon. In the molybdenum furnace, it was sintered at 5 ° C / min to 1350 ° C for 5 h. After cooling, a 0.5 mm thick copper backing was fixed to obtain a cerium-doped titanium dioxide target. (2) The obtained cerium-doped titanium dioxide target was prepared by magnetron sputtering to prepare a cerium-doped titanium dioxide film, wherein the sputtering chamber pressure was 0.3 Pa, the sputtering chamber atmosphere was argon gas, and the substrate was soda-lime-silica glass. A ruthenium-doped titanium dioxide film having a thickness of 360 nm was prepared at a substrate temperature of 25 ° C, a sputtering power of 0.5 W/cm ² , a deposition rate of 4 nm/min, and a sputtering time of 1.5 h. (3) lanthanum-doped titanium dioxide film treated with lanthanum chloride, immersed lanthanum-doped titanium dioxide film in lanthanum chloride solution at 50 ° C for 10 min, then taken out in an inert atmosphere heated to 450 ° C, kept for 30 min, cooled to room temperature A tantalum-doped and antimony-doped titanium dioxide film, that is, a transparent conductive film of this example, is obtained. (4) The obtained conductive film was ultrasonically washed with detergent, distilled water, acetone, and isopropyl alcohol, and then dried at 80 °C. (5) After the surface of the conductive film is treated by UV/ozone, a 150 nm CdS layer is sputtered, and then 4-5 μm CdTe is deposited by near-space sublimation. After CdCl2 annealing and acid etching, 1-3 nm Cu is evaporated, and finally steamed. The cadmium telluride thin film solar cell in this example was obtained by plating 80 nm Au and annealing at 180 °C.

The obtained solar cell was tested in an AM 1.5G environment (100 mW cm ^-2 ), and the results are shown in Fig. 7. In the figure, curve 1 is a test curve using the transparent conductive film of the present application, and curve 2 is a test using FTO. curve. The open circuit voltage of the battery was 0.753 V, the short circuit current was 22.64 mA/cm ² , the fill factor was 60.65%, and the photoelectric conversion efficiency was 10.34%. The comparative sample was made of FTO as the conductive film, and the open circuit voltage of the battery was 0.772V, the short circuit current was 21.33 mA/cm ² , the filling factor was 67.90%, and the photoelectric conversion efficiency was 11.18%. It can be seen that the transparent conductive film of this example has excellent performance in optoelectronic device applications.

The above content is a further detailed description of the present application in conjunction with the specific embodiments, and the specific implementation of the present application is not limited to the description. It will be apparent to those skilled in the art that the present invention can be made in the form of the present invention without departing from the scope of the present invention.

Claims

A transparent conductive film characterized in that the transparent conductive film is a doped titanium dioxide film, the doping is germanium doping, and germanium and/or germanium doping.
The transparent conductive film according to claim 1, wherein the amount of germanium doping is 0.1-5% by weight, the amount of germanium doping is 0.1-20% of total weight, and the amount of germanium doping is It is 0.1-20% of the total weight.
The transparent conductive film according to claim 1 or 2, wherein the crystal phase of the titanium oxide is an anatase phase.
Use of the transparent conductive film according to any one of claims 1 to 3 in a display screen, a touch screen, a photovoltaic device or an optoelectronic device.
A transparent conductive glass comprising a substrate and a conductive film, wherein the conductive film is the transparent conductive film according to any one of claims 1 to 3, wherein the substrate is glass, quartz, sapphire and an organic film. At least one of them.
A composite electrode comprising the transparent conductive film according to any one of claims 1 to 3.
The method for preparing a transparent conductive film according to any one of claims 1 to 3, which comprises preparing a ruthenium and/or ruthenium-doped titanium dioxide film by magnetron sputtering, and then performing a ruthenium and/or ruthenium-doped titanium oxide film.钌 compound treatment;

The magnetron sputtering method comprises: mixing a tantalum source powder and/or a tantalum source powder with a titanium dioxide powder in a stoichiometric ratio, uniformly grinding, and then calcining at a high temperature to form a doped titania target, which is formed by magnetron sputtering. The tantalum and/or niobium doped titanium dioxide film;

The ruthenium compound treatment comprises: immersing the ruthenium and/or ruthenium-doped titanium dioxide film in a ruthenium compound solution, reacting at 10 to 150 ° C for 10 to 120 minutes, and then placing the ruthenium and/or ruthenium-doped titanium oxide film in a vacuum. Or an inert atmosphere or a reducing atmosphere, kept at 100 to 650 ° C for 0-10 h, and cooled to room temperature to obtain a ruthenium doping, and a ruthenium and/or ruthenium doped titanium dioxide film.
The method for preparing a transparent conductive film according to any one of claims 1 to 3, which comprises dispersing a source of germanium and/or germanium with a source of germanium and a source of titanium in a stoichiometric ratio to a solvent. The thermal reaction is carried out under air or an inert atmosphere, and the reaction product is coated on a substrate, and the solvent is dried to obtain a ruthenium doping, and a ruthenium and/or ruthenium-doped titanium oxide film.
The method for preparing a transparent conductive film according to any one of claims 1 to 3, which comprises dispersing a source of germanium and/or germanium with a source of titanium in a stoichiometric ratio to a solvent, in air or inert Performing a thermal reaction under an atmosphere, coating the reaction product on a substrate, drying the solvent to obtain the ruthenium and/or ruthenium-doped titanium dioxide film; and immersing the ruthenium and/or ruthenium-doped titanium dioxide film in the ruthenium compound solution Reacting at 10 to 150 ° C for 10 to 120 minutes, then placing the ruthenium and/or ruthenium-doped titanium dioxide film under vacuum or inert In an atmosphere or a reducing atmosphere, the film is kept at 100 to 650 ° C for 0 to 10 hours, and cooled to room temperature to obtain a cerium doped film, and a cerium and/or cerium doped titanium dioxide film.
The preparation method according to claim 8 or 9, wherein the cerium source is at least one of cerium chloride, cerium ethoxide, nano cerium powder and antimony pentoxide; At least one of ethanol cerium, nano cerium powder, antimony pentoxide, and methanol hydrazine; the titanium source is at least one of n-butyl titanate, isopropyl titanate, and tetraethyl titanate; The solvent is at least one of distilled water, ethanol, n-butanol, acetonitrile, methanol, 2-methoxyethanol, isopropanol, ethylene glycol, N,N-dimethylformamide and tetrahydrofuran; At least one of a halogen cerium, a cerium oxide, a cerium salt, and a cerium organic compound.