CN112951930B - Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof - Google Patents

Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof Download PDF

Info

Publication number
CN112951930B
CN112951930B CN202110128167.6A CN202110128167A CN112951930B CN 112951930 B CN112951930 B CN 112951930B CN 202110128167 A CN202110128167 A CN 202110128167A CN 112951930 B CN112951930 B CN 112951930B
Authority
CN
China
Prior art keywords
titanium dioxide
silver
film
sputtering
plasma
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110128167.6A
Other languages
Chinese (zh)
Other versions
CN112951930A (en
Inventor
宋安刚
霍方方
朱地
胡俊华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Energy Research Institute of Shandong Academy of Sciences
Original Assignee
Energy Research Institute of Shandong Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Energy Research Institute of Shandong Academy of Sciences filed Critical Energy Research Institute of Shandong Academy of Sciences
Priority to CN202110128167.6A priority Critical patent/CN112951930B/en
Publication of CN112951930A publication Critical patent/CN112951930A/en
Application granted granted Critical
Publication of CN112951930B publication Critical patent/CN112951930B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

The disclosure relates to the technical field of electronic materials, and particularly provides a titanium dioxide/silver/titanium dioxide transparent conductive film and a preparation method and application thereof. The silver layer is a pure silver layer, and the thickness change of the silver layer corresponds to different photoelectric properties. The preparation method comprises the following steps: argon is taken as a plasma gas source, oxygen is taken as a reaction gas, a layer of titanium dioxide film is firstly deposited on a substrate by reactive sputtering by adopting a far-source plasma sputtering technology, then a layer of pure silver film is sputtered on the titanium dioxide film by direct current, the oxygen flow and the sputtering power are controlled in the sputtering process, and finally a layer of titanium dioxide film is sputtered on the basis of the control, so that the silver-doped titanium dioxide film is obtained. The problems that in the prior art, the transparent conductive film is often doped with F, so that the preparation process is difficult to operate, the cost is high, toxicity is caused, and certain requirements on waste treatment are met are solved.

Description

Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof
Technical Field
The disclosure relates to the technical field of electronic materials, and particularly provides a titanium dioxide/silver/titanium dioxide transparent conductive film and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
With the development of science and technology and the continuous improvement of the living standard of people, the wide application of high resolution, large-size flat panel displays, solar cells, energy-saving infrared reflection films, electrochromic windows and the like, the demand on transparent conductive films is increasing. The transparent conductive film is required to have not only good conductivity but also excellent visible light transmittance. From the physical point of view, the light transmittance and the electrical conductivity of a substance are a pair of basic contradictions. The transparent conductive film combines the transparency and the conductivity into a film with characteristics in functional materials, and has wide application prospects in the photoelectric industry. In order for a material to have the conductivity generally described, it is necessary to offset the center of its fermi sphere from the origin of the momentum space, i.e., the energy levels in the fermi sphere and its vicinity are very densely distributed according to the band theory, and there is no energy gap between the energy level occupied by electrons and the empty level. When incident light enters, the photoelectric effect is easy to generate, and light is attenuated due to the energy loss of the excited electrons. Therefore, the internal photoelectric effect is not desirable from the viewpoint of light transmittance, and the forbidden band width must be larger than the photon energy.
In order to maintain good visible light transmittance, a broadband transparent conductive oxide semiconductor needs to have a plasma frequency lower than a visible light frequency, and needs to have a constant carrier concentration in order to maintain a constant conductivity, and the plasma frequency is proportional to the carrier concentration. The development of transparent conductive films is based on how to make the two better organic. Since the first discovery that both light transmittance and conductivity can coexist in a Transparent Conductive Oxide (TCO), the development of new TCOs and the design of composite multilayer films have been around such a pair of lances. The TCO can control a band gap structure, carrier concentration and mobility, a work function, and the like by component adjustment to unify contradictions between light transmittance and conductivity. Because the application of a single metal film is limited due to poor light transmission, a composite multilayer film is formed by the single metal film and a dielectric medium with high refractive index, so that the conductivity of the metal and the light transmission of the antireflection film are organically combined, and the later developed composite of the TCO with high refractive index and the metal also obtains good matching of the light transmission and the conductivity. According to different materials, the early researches can divide the materials into a metal transparent conductive film, an oxide transparent conductive film (TCO), a non-oxide transparent conductive film and a polymer transparent conductive film.
In recent years, the film technology is developed rapidly, and the industrial production is partially realized in the aspect of transparent conductive films. SnO was successively developed since the first preparation of transparent conductive cadmium oxide films by thermal oxidation of sputtered cadmium in 1907 Bakdekekeker 2 Base thin film In 2 O 3 Different types of transparent conductive film materials such as base films and the like are applied in a plurality of fields, and a certain market scale is formed.The most widely used is ITO film, but the preparation process and application of the film have great disadvantages, namely, the toxicity of In and the scarcity of In resources cause high production cost, so that the application of ITO film In the future is greatly restricted In the long term, and another widely used transparent conductive film is FTO film.
However, the inventor finds that the film is mostly used as a transparent electrode of a thin film solar cell at present, but the film has certain defects that F is corrosive, so that the preparation is not easy to cost, and the preparation process is toxic due to F doping, so that the treatment of waste is also required. In addition, most of the transparent conductive films in commercial use require high deposition temperature or post annealing treatment to achieve the desired photoelectric properties, which results in complicated process and high cost. It is also difficult to prepare transparent conductive films on flexible substrates (such as PET or PEN) that cannot withstand high temperatures.
Disclosure of Invention
The method aims at solving the problems that the transparent conductive film is often doped with F in the prior art, so that the preparation process is not easy to operate, the cost is high, toxicity is caused, and certain requirements are also met for waste treatment.
In one or some embodiments of the present disclosure, a titanium dioxide/silver/titanium dioxide transparent conductive film is provided, the silver layer is a pure silver layer, and the thickness variation of the silver layer corresponds to different photoelectric properties.
In one or some embodiments of the present disclosure, a method for preparing a titanium dioxide/silver/titanium dioxide transparent conductive film is provided, which includes the following steps: argon is taken as a plasma gas source, oxygen is taken as a reaction gas, a layer of titanium dioxide film is firstly deposited on a substrate by reactive sputtering by adopting a far-source plasma sputtering technology, then a layer of pure silver film is sputtered on the titanium dioxide film by direct current, the oxygen flow and the sputtering power are controlled in the sputtering process, and finally a layer of titanium dioxide film is sputtered on the basis of the control, so that the silver-doped titanium dioxide film is obtained.
In one or more embodiments of the present disclosure, there is provided a use of the above titanium dioxide/silver/titanium dioxide transparent conductive film or the product prepared by the above method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film in a thin film solar cell.
In one or some embodiments of the present disclosure, the application of the titanium dioxide/silver/titanium dioxide transparent conductive film or the product prepared by the preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film as the TCO film is provided.
One or some of the above technical solutions have the following advantages or beneficial effects:
1) The preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film adopts a far-source plasma sputtering technology to perform direct-current sputtering deposition on a substrate to obtain a film, and regulates and controls the photoelectric property of the transparent conductive film by controlling the oxygen flow and the sputtering power in the reactive sputtering process and controlling the thickness of the intermediate layer silver film under the conditions of relatively low sputtering power and oxygen flow; the titanium dioxide/silver/titanium dioxide transparent conductive film is compact and uniform, has good chemical stability and mechanical strength, high light transmittance in a visible light range, low resistivity and good photoelectric property. The preparation method has the advantages of high sputtering speed, low sputtering temperature, good repeatability, low energy consumption and low production cost, and is suitable for popularization and application.
2) The transparent conductive film obtained by the invention is compact and uniform, has good chemical stability, mechanical strength and photoelectric property, and has carrier concentration as high as 10 22 cm 2 Vs, carrier mobility up to 10cm 2 V -1 s -1 Resistivity of 10 -5 Omega cm order of magnitude, and the visible light transmittance is more than 90 percent. The preparation method has the advantages of high sputtering speed, low sputtering temperature, good repeatability, low energy consumption and low production cost, and is suitable for popularization and application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to be construed as limiting the disclosure.
FIG. 1 is a schematic diagram of a remote source plasma sputtering system used in an embodiment;
FIG. 2 is X-ray diffraction patterns of the deposited titanium dioxide/silver/titanium dioxide transparent conductive film at different thicknesses of the intermediate silver film;
FIG. 3 is a Scanning Electron Microscope (SEM) chromatogram of the titanium dioxide/silver/titanium dioxide transparent conductive film of example 4 at different magnifications;
FIG. 4 is a graph showing the results of detecting the transmittance of visible light at different deposition times of the silver thin film of the intermediate layer, including the titanium dioxide/silver/titanium dioxide transparent conductive thin films of examples 1, 2, 3, 4, 5 and 6;
FIG. 5 is a graph showing the electrical properties of the as-deposited titanium dioxide/silver/titanium dioxide transparent conductive films comprising examples 1, 2, 3, 4, 5 and 6 at different thicknesses of the silver film in the intermediate layer;
FIG. 6 is a graph showing the results of sheet resistance measurements of the as-deposited titanium dioxide/silver/titanium dioxide transparent conductive films comprising examples 1, 2, 3, 4, 5 and 6 at different thicknesses of the silver film in the intermediate layer;
FIG. 7 shows the results of current-voltage curve measurements of different thicknesses of the intermediate silver film comprising the as-deposited titanium dioxide/silver/titanium dioxide transparent conductive films of examples 1, 2, 3, 4, 5 and 6;
FIG. 8 is an X-ray diffraction pattern of a pure titanium dioxide film annealed at 450 deg.C;
fig. 9 shows the electrical properties of the titanium dioxide/silver/titanium dioxide transparent conductive film at different thicknesses of the intermediate silver film, which are hall mobility, carrier concentration, and resistivity in sequence from top to bottom.
Wherein: 1. a plasma source emission system; 2. a radio frequency antenna coil; 3. a substrate sample holder; 4. a reaction gas path; 5. an electromagnet; 6. a target material; 7. circulating water; 8. a copper plate; 9. a vacuum chamber; 10 quartz tube.
Detailed Description
The technical solutions in the embodiments of the present disclosure will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the disclosure without making any creative effort, shall fall within the protection scope of the disclosure.
The method aims at the problems that in the prior art, the transparent conductive film is often doped with F, so that the preparation process is not easy to operate, the cost is high, toxicity is caused, and certain requirements are also met on waste treatment.
In one or some embodiments of the present disclosure, a titanium dioxide/silver/titanium dioxide transparent conductive film is provided, where the silver layer is a pure silver layer, and the thickness variation of the silver layer corresponds to different photoelectric properties;
preferably, an increase in silver layer thickness decreases the resistivity and increases the transmittance, and vice versa.
Preferably, the titanium dioxide/silver/titanium dioxide transparent conductive film is in an amorphous structure or a mixture of amorphous and crystalline structures.
Preferably, the method comprises the following steps:
in one or some embodiments of the present disclosure, a method for preparing a titanium dioxide/silver/titanium dioxide transparent conductive film is provided, which includes the following steps: argon is taken as a plasma gas source, oxygen is taken as a reaction gas, a layer of titanium dioxide film is firstly deposited on a substrate by reactive sputtering by adopting a far-source plasma sputtering technology, then a layer of pure silver film is sputtered on the titanium dioxide film by direct current, the oxygen flow and the sputtering power are controlled in the sputtering process, and finally a layer of titanium dioxide film is sputtered on the basis of the control, so that the silver-doped titanium dioxide film is obtained.
The remote source plasma sputtering technique (HiTUS) is a sputtering technique with high target utilization rate, which accomplishes sputtering by high-density plasma generated remotely from the target. In The prior art, a Plasma emission System (PLS) is fixed on a sidewall of a vacuum chamber (sputtering chamber) of a remote Plasma sputtering System corresponding to The remote Plasma sputtering System, that is, a radio frequency coil antenna is wound outside a quartz glass tube; plasma is generated by the plasma, amplified by a transmitting electromagnetic coil at the outlet of the PLS, and focused and controlled by a bunching electromagnetic coil. By fine control of the current to each of the solenoids, the plasma beam can be directed so as to cover the entire surface of the target. Under the condition, argon ions on the surface of the target materialAt low energy (30-50 eV) and high density (ion number 1012-1014/cm) 3 ) Status. Therefore, the target material is uniformly etched, the target poisoning phenomenon is greatly reduced compared with the conventional magnetron sputtering, and the deposition rate of the sputtering deposition film is greatly improved.
Preferably, the sputtering target is a high-purity titanium and silver metal target;
preferably, the argon gas flow in the titanium dioxide reactive sputtering process is 60-70sccm, preferably 70sccm, the oxygen gas flow is 4-5sccm, preferably 4.5sccm, the plasma emission source power is 1000-1500W, preferably 1200W, and the target accelerating bias power is 300-500W, preferably 400W;
preferably, the reactive sputtering time of the two layers of titanium dioxide is 4-7min, preferably 5min, and the thickness is 90-110nm, preferably 100nm;
preferably, the sputtering time of the direct current sputtering silver film is 0-90s, 0s is not contained, the thickness of the silver film is about 0-15nm, 0nm is not contained; the argon flow in the sputtering process is 65-75sccm, preferably 70sccm;
preferably, the plasma emission source power is 450 to 550W, preferably 500W, and the target accelerating bias power is 50 to 150W, preferably 100W.
Preferably, the method specifically comprises the following steps:
1) Firstly, fixing a substrate on a sample rack, then placing the substrate into a cavity, then closing a cabin door, starting vacuumizing, and zeroing a system in the vacuumizing process;
2) Introducing argon into the vacuum cavity, and waiting for the pressure in the vacuum cavity to tend to be stable;
3) Opening a plasma emission power supply to enable argon to form plasma in the vacuum quartz tube, then opening an electromagnet power supply to enable irregular plasma to form plasma beams in the cavity, filling the cavity with the generated plasma beams, then opening a substrate baffle plate to start cleaning the substrate;
4) After the substrate is cleaned, closing the baffle, turning on the power supply of the electromagnetic coil, turning on the target accelerating power supply, and enabling the plasma to bombard the target, namely cleaning the target;
5) Then opening a substrate baffle plate, and formally starting a film deposition process;
6) And after the film deposition is finished, closing the substrate baffle, then closing the target accelerating power supply, closing the plasma emission power supply, closing the electromagnetic coil power supply and the like, when the temperature in the cavity is reduced to the room temperature for about half an hour, breaking the vacuum at the moment, and then taking out the film sample to obtain a finished product.
The particles bombarded by the plasma beam on the target material cannot be directly sputtered on the substrate with a certain distance, but stay and suspend near the surface of the target material, and a proper accelerating voltage needs to be applied to the charged ions to enable the charged ions to fly to the surface of the substrate. The reactive sputtering in the step 1) is to continuously introduce oxygen as a reaction gas in the sputtering process, combine the oxygen with sputtered target particles in the air and react with the sputtered target particles, fly to the substrate in the form of a reaction product under the action of an accelerating bias voltage provided for the bottom of the target and adhere to the surface of the substrate, and deposit to form a layer of compact nano film.
The substrate in the step 1) is glass or a flexible substrate.
The glass substrate is cleaned before use, wherein the cleaning is to place the glass substrate in acetone, isopropyl ketone, ethanol and deionized water in sequence for ultrasonic cleaning, the cleaning time is 15-25 min each time, and the cleaning temperature is 45-55 ℃. And cleaning, airing or wiping by using a dust-free cloth, putting into a sputtering cavity of a remote source plasma sputtering system, and preparing for sputtering.
Before reactive sputtering, the sputtering cavity is vacuumized to 9 x 10 -6 mbar. Then argon gas with a certain flow is introduced into the cavity, and oxygen is introduced after the pressure in the cavity is kept stable. The argon and oxygen are high-purity gases with the purity of not less than 99.999 percent.
Preferably, the vacuum degree of the cavity in the step 1) is (8-10) multiplied by 10 -6 mbar, preferably 9X 10 -6 mbar；
Or, the flow rate of the argon introduced in the step 2) is 65-75sccm, preferably 70sccm, and the pressure in the vacuum cavity is stabilized at 3.5-4.5 × 10 -3 mbar, preferably 4X 10 -3 mbar；
Or, the power of the plasma source radio frequency power supply in the step 3) is 1000-1500W, preferably 1200W when depositing titanium dioxide, 450-650W, preferably 500W when depositing silver, and the time for cleaning the substrate is 2-5min, preferably 3min;
or, the target accelerating power is 350-450W, preferably 400W when the titanium dioxide film is deposited in the step 4), the target accelerating power is 90-110W, preferably 100W when the silver film is deposited, and the cleaning time is 9-11min, preferably 10min.
Preferably, the thin film deposition step comprises:
1, firstly introducing oxygen into a cavity, then preparing a pure titanium dioxide transparent conductive film by a reactive sputtering method,
2, closing the oxygen flow, rotating the target material to a pure silver metal target material after the air pressure of the cavity is stable, preparing a pure silver film by a direct current sputtering method,
and 3, introducing oxygen again, and preparing the pure titanium dioxide transparent conductive film by a reactive sputtering method to obtain the titanium dioxide/silver/titanium dioxide multilayer transparent conductive film with the sandwich structure.
Preferably, in step 1>, the oxygen flow rate is 4.5sccm,
or, in the step 1>, the reactive sputtering time is 5min,
or, in the step 1>, the thickness of the film is 50nm,
or, in the step 3>, the oxygen flow rate is 4.5sccm,
or in the step 3>, the reactive sputtering time is 5min.
Preferably, the deposition temperature is normal temperature. In the reactive sputtering process, the sputtering temperature is 20-50 ℃, and the temperature of the substrate is normal temperature. The process of reactive sputtering deposition of the film is carried out at normal temperature or lower temperature, the substrate does not need to be heated, and the sputtering process is simpler and easy to control.
In the step 2), the temperature in the cavity is naturally cooled to room temperature, wherein the room temperature is 25-30 ℃.
In one or more embodiments of the present disclosure, there is provided a use of the above titanium dioxide/silver/titanium dioxide transparent conductive film or the product prepared by the above method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film in a thin film solar cell.
In one or some embodiments of the present disclosure, there is provided a use of the titanium dioxide/silver/titanium dioxide transparent conductive film or the product obtained by the preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film as a TCO film.
In some embodiments, the remote source plasma sputtering system is mainly composed of a plasma source emission system 1, a vacuum system, a plasma bunching electromagnet, a substrate sample holder 3, a target accelerating bias power supply, a reaction gas path 4, a water cooling system, an air compressor, and the like, as shown in fig. 1. The vacuum system is composed of a vacuum chamber 9, a mechanical pump and a molecular pump, when the system is vacuumized, the mechanical pump is required to be firstly used for pumping to a certain vacuum degree, then the molecular pump is started, the molecular pump is used for directly pumping the gas in the vacuum chamber, the mechanical pump pumps the molecular pump when the molecular pump works, the two vacuum pumps transmit the gas in the vacuum chamber 9 to be pumped to the atmosphere, and therefore a high vacuum degree in the chamber can be guaranteed.
As shown in fig. 1, the left side of the vacuum chamber 9 is connected to the plasma source emission system 1; the plasma source emission system 1 is composed of a radio frequency antenna coil 2 and a quartz tube 10, wherein the radio frequency antenna coil 2 is uniformly wound on the periphery of the quartz tube 10 and has a certain uniform distance from the quartz tube 10. When plasma needs to be generated, high-purity argon gas with a certain flow is continuously introduced into the vacuum chamber 9, so that the air pressure in the chamber is stabilized at a required pressure, then the radio frequency antenna coil 2 is electrified, and under the action of a high-frequency radio frequency power supply, electrons and neutral particles in the quartz tube 10 keep a high collision rate, so that argon gas molecules are ionized, and light purple plasma can be generated in the quartz tube 10.
An electromagnet 5 for controlling the shape and the moving direction of the plasma beam, called a plasma bunching electromagnet coil, is respectively installed on one side of the quartz tube 10 of the plasma source emission system 1 close to the vacuum chamber 9 and below the target 6. The plasma generated by the plasma source is continuously delivered to the vacuum chamber 9 by activating the electromagnet 5 on one side of the vacuum chamber to generate the desired magnetic field line distribution before the rf power is turned on to generate the plasma. When the electromagnet 5 below the target does not work, the generated plasma is dispersedly distributed in the whole vacuum chamber 9, when the electromagnet 5 is electrified and generates a magnetic field, the shape of magnetic lines of force in the effective area is changed, the plasma moves along the magnetic lines of force according to the guiding action of the magnetic field, and the plasma is changed into a uniform light beam as a whole and is bent along with the magnetic field and directly and intensively hit the surface of the target 6. The shape of the magnetic lines of force is precisely controlled by adjusting the two electromagnets 5 to appropriate currents, so that the plasma beam can be guided to cover exactly the entire area of the target 6. As the plasma is applied to the surface of the target material, the target material 6 can generate more heat, in order to protect the target material and prevent the target material from being melted, circulating water 7 continuously flows in the copper plate 8 below the target material to take away the heat, and the circulating water 7 is radiated by an external water cooling machine and is kept at the level of room temperature.
The energy of the plasma beam on the target is about 10eV, and the ejected particles cannot be directly sputtered onto a substrate with a certain distance, but stay suspended near the surface of the target, so that a proper accelerating voltage needs to be applied to the charged particles to enable the charged particles to fly to the surface of the substrate. The method used in the invention is a reactive sputtering method, as shown in figure 2, reaction gas is introduced in the sputtering process, the reaction gas and sputtered target particles are combined and react in the air, and fly to the substrate in the form of reaction products under the action of an accelerating bias voltage provided for the bottom of the target and are adhered to the surface of the substrate, and a layer of compact nano film can be formed after a certain time.
The substrate sample holder is used for fixing a substrate, and an openable or closable baffle plate is arranged below the substrate sample holder and is used for being tightly attached to the lower surface of the substrate so as to control the beginning or the end of reactive sputtering deposition on the surface of the substrate.
In a specific embodiment, the target material used is pure metal, and the target material has a size of 3 inches in diameter and 6mm in thickness.
The target generates heat in the sputtering process, the target generates excessive heat and generates expansion and contraction due to excessive heat and even possibly cracks and scraps the target, the target needs to be pre-sputtered before a film is deposited by reactive sputtering in order to prolong the service life of the target and protect the target, the bias applied to the target starts from a lower value (the power of the target is 50W), and then is gradually increased at an interval of 50W until the required bias power of the target is increased. The target material pre-sputtering also plays a role in cleaning the target material, so that an oxide layer or pollutants possibly appearing on the surface of the target material are sputtered off, and the purity of the raw material is ensured.
Example 1
The preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film comprises the following steps:
1) Cleaning a substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) Sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 9 x 10 -6 mbar, introducing argon of 70sccm into the chamber, and starting a plasma source emission system after the pressure in the chamber is kept stable so as to generate plasma at the plasma source; starting a plasma bunching electromagnet to enable the target to be bombarded by the plasma, and pre-sputtering the target;
introducing oxygen into the chamber, wherein the flow rate of the oxygen is 4.5sccm, and the pressure in the sputtering chamber is 3.7 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, the baffle plate tightly attached to the lower part of the glass substrate is opened to start to enterPerforming reactive sputtering deposition on the film;
in the process of reactive sputtering of the titanium dioxide film, the power of a plasma emission source is 1200W, the accelerated bias power of a target material is 400W, the sputtering speed is 10nm/min, the reactive sputtering time of the titanium dioxide on the upper layer and the titanium dioxide on the lower layer is 5min, the thickness is 100nm in total, when the silver film is sputtered by direct current, the power of the plasma emission source is 500W, the accelerated bias power of the target material is 100W, the sputtering time of the silver film sputtered by direct current is 24s, the thickness of the silver film is 4nm, the sputtering temperature is 20 ℃, and the substrate temperature is normal temperature;
and after sputtering is finished, closing the baffle below the glass substrate, depositing a layer of nano film on the glass substrate to obtain a finished product, and naturally cooling to room temperature to obtain the titanium dioxide/silver/titanium dioxide transparent conductive film.
Through detection, the light transmittance of the titanium dioxide/silver/titanium dioxide transparent conductive film obtained in the embodiment is more than 70%, and the resistivity is as low as 3.06 multiplied by 10 -4 Ω · cm, and a square resistance of 30.6 Ω.
Example 2
The preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film comprises the following steps:
1) Cleaning a substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for preparing sputtering;
2) Sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 9 x 10 -6 mbar, introducing argon of 70sccm into the chamber, and starting a plasma source emission system after the pressure in the chamber is kept stable so as to generate plasma at the plasma source; the plasma bunching electromagnet is started to make the plasma bombard the target material and aim at the target materialCarrying out pre-sputtering;
introducing oxygen into the chamber, wherein the flow rate of the oxygen is 4.5sccm, and the pressure in the sputtering chamber is 3.7 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the process of reactive sputtering of the titanium dioxide film, the power of a plasma emission source is 1200W, the accelerated bias power of a target material is 400W, the sputtering speed is 10nm/min, the reactive sputtering time of the titanium dioxide on the upper layer and the titanium dioxide on the lower layer is 5min, the thickness is 100nm in total, when the silver film is sputtered by direct current, the power of the plasma emission source is 500W, the accelerated bias power of the target material is 100W, the sputtering time of the direct current sputtering silver film is 36s, the thickness of the silver film is 6nm, the sputtering temperature is 20 ℃, and the temperature of a substrate is normal temperature;
and after sputtering is finished, closing the baffle below the glass substrate, depositing a layer of nano film on the glass substrate to obtain a finished product, and naturally cooling to room temperature to obtain the titanium dioxide/silver/titanium dioxide transparent conductive film.
Through detection, the light transmittance of the titanium dioxide/silver/titanium dioxide transparent conductive film obtained in the embodiment is more than 80%, and the resistivity is as low as 1.95 × 10 -4 Ω · cm, and a square resistance of 19.5 Ω.
Example 3
The preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film of the embodiment comprises the following steps:
1) Cleaning a substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) Sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and specifically comprises the following steps:
reactive sputteringPreviously, the sputtering chamber of a remote source plasma sputtering system was evacuated to a vacuum of 9X 10 -6 mbar, introducing argon of 70sccm into the chamber, and starting a plasma source emission system after the pressure in the chamber is kept stable so as to generate plasma at the plasma source; starting a plasma bunching electromagnet to enable the plasma to bombard the target material and pre-sputter the target material;
introducing oxygen into the chamber, wherein the flow rate of the oxygen is 4.5sccm, and the pressure in the sputtering chamber is 3.7 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the process of reactive sputtering of the titanium dioxide film, the power of a plasma emission source is 1200W, the accelerated bias power of a target material is 400W, the sputtering speed is 10nm/min, the reactive sputtering time of the titanium dioxide on the upper layer and the titanium dioxide on the lower layer is 5min, the thickness is 100nm in total, when the silver film is sputtered by direct current, the power of the plasma emission source is 500W, the accelerated bias power of the target material is 100W, the sputtering time of the silver film sputtered by direct current is 48s, the thickness of the silver film is 8nm, the sputtering temperature is 20 ℃, and the substrate temperature is normal temperature;
and after sputtering is finished, closing the baffle below the glass substrate, depositing a layer of nano film on the glass substrate to obtain a finished product, and naturally cooling to room temperature to obtain the titanium dioxide/silver/titanium dioxide transparent conductive film.
Through detection, the light transmittance of the titanium dioxide/silver/titanium dioxide transparent conductive film obtained in the embodiment is more than 90%, and the resistivity is as low as 9.26 × 10 -5 Ω · cm, and a square resistance of 9.26 Ω.
Example 4
The preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film comprises the following steps:
1) Cleaning a substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) Sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 9 x 10 -6 mbar, introducing argon of 70sccm into the cavity, and starting a plasma source emission system after the pressure in the cavity is kept stable so that plasma is generated at the plasma source; starting a plasma bunching electromagnet to enable the target to be bombarded by the plasma, and pre-sputtering the target;
introducing oxygen into the chamber, wherein the flow rate of the oxygen is 4.5sccm, and the pressure in the sputtering chamber is 3.7 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the process of reactive sputtering of the titanium dioxide film, the power of a plasma emission source is 1200W, the accelerated bias power of a target material is 400W, the sputtering speed is 10nm/min, the reactive sputtering time of the titanium dioxide of the upper layer and the titanium dioxide of the lower layer are 5min, the thickness is 100nm in total, when the silver film is sputtered by direct current, the power of the plasma emission source is 500W, the accelerated bias power of the target material is 100W, the sputtering time of the silver film sputtered by direct current is 60s, the thickness of the silver film is 10nm, the sputtering temperature is 20 ℃, and the substrate temperature is normal temperature;
and after sputtering is finished, closing the baffle below the glass substrate, depositing a layer of nano film on the glass substrate to obtain a finished product, and naturally cooling to room temperature to obtain the titanium dioxide/silver/titanium dioxide transparent conductive film.
Through detection, the light transmittance of the titanium dioxide/silver/titanium dioxide transparent conductive film obtained in the embodiment is more than 85%, and the resistivity is as low as 6.37 × 10 -5 Ω · cm, and a square resistance of 6.06 Ω.
FIG. 3 is SEM images of the as-deposited film at different magnifications, and it can be seen that the surface of the film is very uniform, flat and smooth, and has no impurities or crystallization tendency.
Example 5
The preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film comprises the following steps:
1) Cleaning a substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) Sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 9 x 10 -6 mbar, introducing argon of 70sccm into the chamber, and starting a plasma source emission system after the pressure in the chamber is kept stable so as to generate plasma at the plasma source; starting a plasma bunching electromagnet to enable the plasma to bombard the target material and pre-sputter the target material;
introducing oxygen into the chamber, wherein the flow rate of the oxygen is 4.5sccm, and the pressure in the sputtering chamber is 3.7 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the process of reactive sputtering of the titanium dioxide film, the power of a plasma emission source is 1200W, the accelerated bias power of a target material is 400W, the sputtering speed is 10nm/min, the reactive sputtering time of the titanium dioxide on the upper layer and the titanium dioxide on the lower layer is 5min, the thickness is 100nm in total, when the silver film is sputtered by direct current, the power of the plasma emission source is 500W, the accelerated bias power of the target material is 100W, the sputtering time of the silver film sputtered by direct current is 72s, the thickness of the silver film is 12nm, the sputtering temperature is 20 ℃, and the substrate temperature is normal temperature;
and after sputtering is finished, closing the baffle below the glass substrate, depositing a layer of nano film on the glass substrate to obtain a finished product, and naturally cooling to room temperature to obtain the titanium dioxide/silver/titanium dioxide transparent conductive film.
Through detection, the light transmittance of the titanium dioxide/silver/titanium dioxide transparent conductive film obtained in the embodiment is more than 80%, and the resistivity is as low as 3.22 multiplied by 10 -5 Ω · cm, and a square resistance of 3.75 Ω.
Example 6
The preparation method of the titanium dioxide/silver/titanium dioxide transparent conductive film of the embodiment comprises the following steps:
1) Cleaning the substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) Sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 9 x 10 -6 mbar, introducing argon of 70sccm into the cavity, and starting a plasma source emission system after the pressure in the cavity is kept stable so that plasma is generated at the plasma source; starting a plasma bunching electromagnet to enable the target to be bombarded by the plasma, and pre-sputtering the target;
introducing oxygen into the chamber, wherein the flow rate of the oxygen is 4.5sccm, and the pressure in the sputtering chamber is 3.7 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the process of reactive sputtering of the titanium dioxide film, the power of a plasma emission source is 1200W, the accelerated bias power of a target material is 400W, the sputtering speed is 10nm/min, the reactive sputtering time of the titanium dioxide on the upper layer and the titanium dioxide on the lower layer is 5min, the thickness is 100nm in total, when the silver film is sputtered by direct current, the power of the plasma emission source is 500W, the accelerated bias power of the target material is 100W, the sputtering time of the silver film sputtered by direct current is 84s, the thickness of the silver film is 14nm, the sputtering temperature is 20 ℃, and the substrate temperature is normal temperature;
and after sputtering is finished, closing the baffle below the glass substrate, depositing a layer of nano film on the glass substrate to obtain a finished product, and naturally cooling to room temperature to obtain the titanium dioxide/silver/titanium dioxide transparent conductive film.
Through detection, the light transmittance of the titanium dioxide/silver/titanium dioxide transparent conductive film obtained in the embodiment is more than 80%, and the resistivity is as low as 2.5 × 10 -5 Ω · cm, and a square resistance of 3.06 Ω.
As can be seen from fig. 2, when the silver metal of the intermediate layer is not deposited, the film is in a pure titanium dioxide phase and shows an amorphous state, because thermodynamic conditions for forming titanium dioxide crystals are not satisfied during the sputtering process at normal temperature, atoms in the film cannot nucleate and grow in a limited time, and as the thickness of the silver film of the intermediate layer increases, weak silver nanocrystals appear in the film. The film showed a strong crystallographic orientation on the (111) (200) crystal plane, as seen by comparison with pdf cards. Because the sputtering temperature is low, the transparent conductive film has good application prospect on flexible semiconductor devices, for example, the film can be prepared on flexible substrates (PET, PEN) which do not resist high temperature.
It can be seen from fig. 4 that the thickness of the intermediate silver film has a great influence on the transmittance of the film during the process of preparing the film by sputtering deposition. The light transmittance of the film is gradually increased with the increase of the sputtering time of the silver film. When the thickness of the film is 10nm, the visible light transmittance reaches 90 percent.
As shown in FIG. 5, the film resistivity gradually decreased with the increase of the thickness of the interlayer silver film, and was maintained at 10 when the film thickness was more than 8nm -5 In the order of Ω · cm. The carrier concentration is gradually increased to 10 along with the increase of the thickness of the intermediate layer silver film 21 -10 22 cm -3 The Hall mobility of the film is 5-15cm 2 between/Vs.
It can be seen from fig. 6 that the sheet resistance decreased as the thickness of the intermediate silver film increased during the process of preparing the film by sputter deposition. When the thickness of the intermediate silver film was 10nm, the sheet square resistance was 6.06. Omega.
It can be seen from fig. 7 that all the films are in good ohmic contact with the electrodes due to the good conductivity of the films. The slope of the film current-voltage curve increases with the thickness of the silver film of the intermediate layer.
In order to prove the structure of the upper and lower layers of films, the deposited titanium dioxide film is annealed and tested by X-ray diffraction in FIG. 8, and the crystal structure of the film is pure anatase phase titanium dioxide.
The disclosure of the present invention is not limited to the specific embodiments, but rather to the specific embodiments, the disclosure is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. A preparation method of a titanium dioxide/silver/titanium dioxide transparent conductive film is characterized by comprising the following steps:
argon is used as a plasma gas source, oxygen is used as a reaction gas, a titanium dioxide film is firstly deposited on a substrate by reactive sputtering by adopting a remote source plasma sputtering technology, then a pure silver film is sputtered on the titanium dioxide film by direct current, in the sputtering process, controlling the oxygen flow and the sputtering power to keep stable, controlling the thickness of the silver film by controlling the sputtering time, and finally reactively sputtering a layer of titanium dioxide film on the basis to obtain the silver-coated titanium dioxide film;
the sputtering target is a high-purity titanium and silver metal target;
in the process of reactive sputtering of titanium dioxide, the flow rate of argon is 60-70sccm, the flow rate of oxygen is 4-5sccm, the power of a plasma emission source is 1000-1500W, and the accelerated bias power of a target is 300-500W;
the reactive sputtering time of the two layers of titanium dioxide is 4-7min, and the thickness is 90-110nm;
the sputtering time of the direct current sputtering silver film is 0-90s and does not contain 0s, and the thickness of the silver film is 0-15nm and does not contain 0nm; the argon flow in the sputtering process is 65-75 sccm;
the power of a plasma emission source is 450-550W, and the accelerating bias power of the target is 50-150W;
the titanium dioxide/silver/titanium dioxide transparent conductive film is in an amorphous structure or a mixture of an amorphous structure and a crystal structure.
2. The method for preparing a titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 1, wherein the flow rate of argon is 70sccm, the flow rate of oxygen is 4.5sccm, the power of a plasma emission source is 1200W, and the power of a target accelerating bias is 400W in the process of reactive sputtering of titanium dioxide; the reactive sputtering time of the two layers of titanium dioxide is 5min, and the thickness is 100nm in total; the flow of argon gas in the process of sputtering the silver film by direct current is 70sccm; the plasma emission source power is 500W, and the target accelerating bias power is 100W.
3. The method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 1, which comprises the following steps:
1) Firstly, fixing a substrate on a sample rack, then placing the substrate into a cavity, then closing a cabin door, starting vacuumizing, and zeroing a system in the vacuumizing process;
2) Introducing argon into the vacuum cavity, and waiting for the pressure in the vacuum cavity to tend to be stable;
3) Opening a plasma emission power supply to enable argon to form plasma in the vacuum quartz tube, then opening an electromagnet power supply to enable irregular plasma to form plasma beams in the cavity, filling the cavity with the generated plasma beams, then opening a substrate baffle plate to start cleaning the substrate;
4) After the substrate is cleaned, closing the baffle, turning on the power supply of the electromagnetic coil, turning on the target accelerating power supply, and enabling the plasma to bombard the target, namely cleaning the target;
5) Then opening a substrate baffle plate, and formally starting a film deposition process;
6) And after the film deposition is finished, closing the substrate baffle, then closing the target accelerating power supply, closing the plasma emission power supply, closing the electromagnetic coil power supply, breaking the vacuum when the temperature in the cavity is reduced to the room temperature, and then taking out the film sample to obtain a finished product.
4. The method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 3, wherein the degree of vacuum of the cavity in the step 1) is 8 x 10 -6 -10×10 -6 mbar；
Or, the flow rate of the introduced argon in the step 2) is 65-75sccm, and the pressure in the vacuum cavity is stabilized at 3.5-4.5 multiplied by 10 -3 mbar ；
Or, the power of the plasma source radio frequency power supply in the step 3) is 1000-1500W when depositing titanium dioxide, 450-650W when depositing silver, and the time for cleaning the substrate is 2-5 min;
or, the target accelerating power is 350-450W when the titanium dioxide film is deposited in the step 4), the target accelerating power is 90-110W when the silver film is deposited, and the cleaning time is 9-11 min.
5. The method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 4, wherein the vacuum degree of the cavity in the step 1) is 9 x 10 -6 mbar; the flow of the introduced argon in the step 2) is 70sccm, and the pressure in the vacuum cavity is stabilized at 4 multiplied by 10 -3 mbar; step 3), the power of the plasma source radio frequency power supply is 1200W when depositing titanium dioxide, 500W when depositing silver, and the time for cleaning the substrate is 3min; and 4) depositing a titanium dioxide film, wherein the target accelerating power is 400W, depositing a silver film, the target accelerating power is 100W, and the cleaning time is 10min.
6. The method for preparing a titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 3, wherein the film deposition step comprises:
1, firstly introducing oxygen into the cavity, then preparing a pure titanium dioxide transparent conductive film by a reactive sputtering method,
2, closing the oxygen flow, rotating the target material to a pure silver metal target material after the air pressure of the cavity is stable, preparing a pure silver film by a direct current sputtering method,
and 3, introducing oxygen again, and preparing the pure titanium dioxide transparent conductive film by a reactive sputtering method to obtain the titanium dioxide/silver/titanium dioxide multilayer transparent conductive film with the sandwich structure.
7. The method for preparing a titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 6, wherein in the step 1>, the oxygen flow rate is 4.5sccm,
or, in the step 1>, the reactive sputtering time is 5min,
or, in the step 1>, the thickness of the film is 50nm,
or, in the step 3>, the oxygen flow rate is 4.5sccm,
or, in the step 3>, the reactive sputtering time is 5min.
8. The method for producing a titanium dioxide/silver/titanium dioxide transparent conductive film according to any one of claims 1 to 7, wherein the deposition temperature is room temperature.
CN202110128167.6A 2021-01-29 2021-01-29 Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof Active CN112951930B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110128167.6A CN112951930B (en) 2021-01-29 2021-01-29 Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110128167.6A CN112951930B (en) 2021-01-29 2021-01-29 Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112951930A CN112951930A (en) 2021-06-11
CN112951930B true CN112951930B (en) 2022-11-04

Family

ID=76239954

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110128167.6A Active CN112951930B (en) 2021-01-29 2021-01-29 Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112951930B (en)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU561315B2 (en) * 1984-10-29 1987-05-07 Ppg Industries Ohio, Inc. Sputtering films of metal alloy oxide
US4834857A (en) * 1988-04-01 1989-05-30 Ppg Industries, Inc. Neutral sputtered films of metal alloy oxides
CN1442872A (en) * 2003-04-17 2003-09-17 上海交通大学 Multilayer nano transparent conductive membrane and its preparation method
CN100517517C (en) * 2006-11-22 2009-07-22 鲁东大学 Flexible composite transparent conductive film and Manufacturing method
CN103060782B (en) * 2012-12-26 2015-04-22 中国科学院长春光学精密机械与物理研究所 Preparation method for electrically-conducting transparent TiO2/Ag/TiO2 composite film
CN104766894B (en) * 2015-04-08 2016-08-24 合肥工业大学 A kind of method improving medium/medium/metal electrode optical property
CN106282926A (en) * 2016-09-30 2017-01-04 中国科学院上海硅酸盐研究所 A kind of method that room temperature sputtering method prepares titanium deoxid film
CN106784041A (en) * 2017-02-04 2017-05-31 江苏神科新能源有限公司 A kind of silicon based hetero-junction solar cell and preparation method thereof
CN108878058B (en) * 2018-06-25 2019-11-22 湖北雄华科技有限公司 Three-decker transparent conductive film and preparation method thereof for dimming glass
CN110835740A (en) * 2018-08-17 2020-02-25 广州市思创信息技术有限公司 Preparation method of high-transmission composite Ag film

Also Published As

Publication number Publication date
CN112951930A (en) 2021-06-11

Similar Documents

Publication Publication Date Title
KR100649838B1 (en) Transparent conductive laminate and process of producing the same
CN105821378B (en) A kind of niobium doping stannic oxide transparent conductive film and preparation method thereof
WO2004106581A2 (en) Transparent conductive oxides
JP2004511655A (en) Preparation method of indium tin oxide thin film using magnetron negative ion sputtering source
CN105951053A (en) Production method for titanium dioxide transparent conductive oxide mixed with niobium and titanium dioxide transparent conductive oxide mixed with niobium
Delahoy et al. Deposition schemes for low cost transparent conductors for photovoltaics
Chiang et al. Deposition of high-transmittance ITO thin films on polycarbonate substrates for capacitive-touch applications
Mian et al. Improvement of the uniformity of structural and electrical properties of transparent conductive Al-doped ZnO thin films by inductively coupled plasma-assisted radio frequency magnetron sputtering
Du et al. Synthesis of high-quality AZO polycrystalline films via target bias radio frequency magnetron sputtering
CN102312201B (en) Preparation method of Al-doped zinc oxide transparent conductive thin film
Bae et al. Effects of oxygen ion beam plasma conditions on the properties of Indium tin oxide thin films
Zhu et al. Highly transparent conductive F-doped SnO2 films prepared on polymer substrate by radio frequency reactive magnetron sputtering
JP3697190B2 (en) Solar cell
CN112951930B (en) Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof
JP2003105533A (en) Method of producing transparent electroconductive film and transparent electroconductive film
CN108441833B (en) Multilayer transparent conductive film and preparation method thereof
WO2008072900A1 (en) Transparent conductive membrane of high resistance touch panel of capacitance and manufacture method thereof
Lin et al. The optical and electrical properties of F doped ZnO thin film by different post-annealing temperatures
Jung et al. Process control for low temperature reactive deposition of Al doped ZnO films by ICP-assisted DC magnetron sputtering
CN112941476B (en) Tin dioxide/copper/tin dioxide multilayer transparent conductive film and preparation method and application thereof
CN112941479B (en) Method for adjusting thickness of silver layer by tin dioxide/silver/tin dioxide transparent conductive film and application
Liu et al. High-quality indium tin oxide films prepared at room temperature by oxygen ion beam assisted deposition
CN112941464B (en) Multilayer transparent conductive film and preparation method and application thereof
JP2003086025A (en) Transparent conductive film forming substrate and method for manufacturing the same
CN105908127A (en) P-type doped tin dioxide transparent conductive film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant