CN112951930A - 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 PDFInfo
- Publication number
- CN112951930A CN112951930A CN202110128167.6A CN202110128167A CN112951930A CN 112951930 A CN112951930 A CN 112951930A CN 202110128167 A CN202110128167 A CN 202110128167A CN 112951930 A CN112951930 A CN 112951930A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- silver
- film
- sputtering
- transparent conductive
- 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.)
- Granted
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 331
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 165
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 59
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000000758 substrate Substances 0.000 claims abstract description 104
- 238000004544 sputter deposition Methods 0.000 claims abstract description 102
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052709 silver Inorganic materials 0.000 claims abstract description 63
- 239000004332 silver Substances 0.000 claims abstract description 63
- 238000005546 reactive sputtering Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 50
- 229910052786 argon Inorganic materials 0.000 claims abstract description 37
- 238000002294 plasma sputter deposition Methods 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 23
- 239000012495 reaction gas Substances 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 239000010408 film Substances 0.000 claims description 210
- 239000013077 target material Substances 0.000 claims description 36
- 238000000151 deposition Methods 0.000 claims description 35
- 238000004140 cleaning Methods 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 25
- 238000002834 transmittance Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005477 sputtering target Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 claims 1
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 abstract description 3
- 239000012776 electronic material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 42
- 239000011521 glass Substances 0.000 description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000004506 ultrasonic cleaning Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 8
- 239000002120 nanofilm Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 1
- -1 argon ions Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
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
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 scientific 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 fundamental contradictions. The transparent conductive film is a film with characteristics in functional materials by combining transparency and conductivity, and has wide application prospect 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. The single metal film has poor light transmission, so that the application of the single metal film is limited, and therefore, the single metal film and a dielectric medium with high refractive index are often formed into a composite multilayer film, so that the conductivity of metal and the light transmission of an antireflection film are organically unified, 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. Early studies 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 according to the difference of the materials.
In recent years, the film technology is rapidly developed, 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 Bakdekekeker2Base thin film In2O3Different 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 the doping of F, so that the treatment of wastes 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, 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.
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 form a film, controls the oxygen flow and sputtering power in the reactive sputtering process, and controls the thickness of the intermediate layer silver film to regulate and control the photoelectric property of the transparent conductive 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 1022cm2(vi)/vs, carrier mobility up to 10cm2V-1s-1Resistivity of 10-5Omega 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 incorporated in and constitute a part of this disclosure, illustrate embodiments of the disclosure and, together with the description, serve to explain the disclosure and not to limit 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 atlas 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 measuring the visible light transmittance of the titanium dioxide/silver/titanium dioxide transparent conductive films comprising examples 1, 2, 3, 4, 5 and 6 at different deposition times of the intermediate silver film;
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 is a graph showing 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 after annealing 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 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, 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 and amplified by an emission electromagnetic coil at the outlet of PLS, and the focusing and control of the direction of the plasma are completed by a beam-bunching electromagnetic coil. By fine control of the current to each solenoid, the plasma beam can be directed so as to cover the entire surface of the target. Under the condition, the argon ions on the surface of the target are in 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 flow is 60-70sccm, preferably 70sccm, the oxygen 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 during the reactive sputtering of titanium dioxide;
preferably, the reactive sputtering time of the two layers of titanium dioxide is 4-7min, preferably 5min, and the thickness is 90-110nm, preferably 100 nm;
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 70 sccm;
preferably, the power of the plasma emission source is 450-550W, preferably 500W, and the power of the target accelerating bias voltage is 50-150W, 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 10-6mbar. 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 10-6mbar, preferably 9X 10-6mbar;
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 × 10-3mbar, preferably 4X 10-3mbar;
Or, the power of the plasma source radio frequency power supply in the step 3) is 1000-1500W, preferably 1200W when depositing the titanium dioxide, is 450-650W, preferably 500W when depositing the silver, and the time for cleaning the substrate is 2-5min, preferably 3 min;
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 10 min.
Preferably, the thin 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.
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 5 min.
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 is 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, and is called a plasma bunching electromagnet coil. Before the rf power is turned on to generate the plasma, the electromagnet 5 on the side of the vacuum chamber is activated to generate the desired magnetic field line distribution, so that the plasma generated by the plasma source is continuously delivered to the vacuum chamber 9. 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 on the 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 cold by directly applying an excessively high bias voltage to the target, and even the target is possibly cracked and scrapped, in order to prolong the service life of the target and protect the target, the target needs to be pre-sputtered before a film is deposited by reactive sputtering, the bias voltage applied to the target is started from a lower value (50W of target power), then is gradually increased, and is spaced by 50W in the middle until the target bias power is increased to the required target bias power. The pre-sputtering of the target material 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 specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 9 x 10-6mbar, 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 10-3mbar, 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 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 × 10-4Ω · 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 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 10-6mbar, 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 10-3mbar, 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 36s, the thickness of the silver film is 6nm, 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 1.95 × 10-4Ω · cm, and a square resistance of 19.5 Ω.
Example 3
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 10-6mbar, 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 10-3mbar, 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 × 10-5Ω · 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 specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 9 x 10-6mbar, 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 10-3mbar, 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 openedStarting to perform reactive sputtering deposition of a 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 × 10-5Ω · 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 10-6mbar, then 70sccm argon gas was introduced into the chamberAfter the pressure in the cavity is kept stable, starting a plasma source emission system to enable the plasma source to generate plasma; 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 10-3mbar, 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 × 10-5Ω · cm, and a square resistance of 3.75 Ω.
Example 6
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 10-6mbar, 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 10-3mbar, 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 × 10-5Ω · 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 in 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-5In 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 film21-1022cm-3The Hall mobility of the film is 5-15cm2Vs.
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 increasing thickness of the intermediate silver film.
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 (10)
1. The titanium dioxide/silver/titanium dioxide transparent conductive film is characterized in that the silver layer is a pure silver layer, and the thickness change 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.
2. The titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 1, wherein the titanium dioxide/silver/titanium dioxide transparent conductive film is of an amorphous structure or a mixture of an amorphous and a crystalline structure.
3. A preparation method of a titanium dioxide/silver/titanium dioxide transparent conductive film is characterized by comprising the following steps:
argon is taken as a plasma gas source, oxygen is taken as a reaction gas, a titanium dioxide film is firstly deposited on a substrate by reactive sputtering by adopting a far-source plasma sputtering technology, then a pure silver film is sputtered on the titanium dioxide film by direct current, the oxygen flow and the sputtering power are controlled to be stable in the sputtering process, the thickness of the silver film is controlled by controlling the sputtering time, and finally a titanium dioxide film is sputtered by reaction on the basis to obtain the silver-silver;
preferably, the sputtering target is a high-purity titanium and silver metal target;
preferably, the argon flow is 60-70sccm, preferably 70sccm, the oxygen 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 during the reactive sputtering of titanium dioxide;
preferably, the reactive sputtering time of the two layers of titanium dioxide is 4-7min, preferably 5min, and the thickness is 90-110nm, preferably 100 nm;
preferably, the sputtering time of the direct current sputtering silver film is 0-90s and is free of 0s, and the thickness of the silver film is 0-15nm and is free of 0 nm; the argon flow in the sputtering process is 65-75sccm, preferably 70 sccm;
preferably, the power of the plasma emission source is 450-550W, preferably 500W, and the power of the target accelerating bias voltage is 50-150W, preferably 100W.
4. The method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 3, 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 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.
5. The method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 4, wherein the degree of vacuum of the cavity in step 1) is 8-10 x 10-6mbar, preferably 9X 10-6mbar;
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 × 10-3mbar, preferably 4X 10-3mbar;
Or, the power of the plasma source radio frequency power supply in the step 3) is 1000-1500W, preferably 1200W when depositing the titanium dioxide, is 450-650W, preferably 500W when depositing the silver, and the time for cleaning the substrate is 2-5min, preferably 3 min;
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 10 min.
6. The method for preparing a titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 4, 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 5 min.
8. The method for producing a titanium dioxide/silver/titanium dioxide transparent conductive film according to any one of claims 3 to 7, wherein the deposition temperature is normal temperature.
9. Use of the titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 1 or 2 or the product obtained by the method for preparing the titanium dioxide/silver/titanium dioxide transparent conductive film according to any one of claims 3 to 8 in a thin film solar cell.
10. Use of the product of the process for the preparation of a titanium dioxide/silver/titanium dioxide transparent conductive film according to claim 1 or 2 or of a titanium dioxide/silver/titanium dioxide transparent conductive film according to any one of claims 3 to 8 as a TCO film.
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 true CN112951930A (en) | 2021-06-11 |
CN112951930B 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) |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN85109342A (en) * | 1984-10-29 | 1986-10-08 | Ppg工业公司 | Sputtered film of metal alloy oxide |
CN1037550A (en) * | 1988-04-01 | 1989-11-29 | Ppg工业公司 | The neutral sputtered film of metal alloy oxide |
CN1442872A (en) * | 2003-04-17 | 2003-09-17 | 上海交通大学 | Multilayer nano transparent conductive membrane and its preparation method |
CN1979695A (en) * | 2006-11-22 | 2007-06-13 | 鲁东大学 | Flexible composite transparent conductive film and mfg. method |
CN103060782A (en) * | 2012-12-26 | 2013-04-24 | 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 |
CN104766894A (en) * | 2015-04-08 | 2015-07-08 | 合肥工业大学 | Method for improving photoelectric property of dielectric/metal/dielectric electrodes |
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 |
CN108878058A (en) * | 2018-06-25 | 2018-11-23 | 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 |
-
2021
- 2021-01-29 CN CN202110128167.6A patent/CN112951930B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN85109342A (en) * | 1984-10-29 | 1986-10-08 | Ppg工业公司 | Sputtered film of metal alloy oxide |
CN1037550A (en) * | 1988-04-01 | 1989-11-29 | Ppg工业公司 | The neutral sputtered film of metal alloy oxide |
CN1442872A (en) * | 2003-04-17 | 2003-09-17 | 上海交通大学 | Multilayer nano transparent conductive membrane and its preparation method |
CN1979695A (en) * | 2006-11-22 | 2007-06-13 | 鲁东大学 | Flexible composite transparent conductive film and mfg. method |
CN103060782A (en) * | 2012-12-26 | 2013-04-24 | 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 |
CN104766894A (en) * | 2015-04-08 | 2015-07-08 | 合肥工业大学 | Method for improving photoelectric property of dielectric/metal/dielectric electrodes |
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 |
CN108878058A (en) * | 2018-06-25 | 2018-11-23 | 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 |
Non-Patent Citations (2)
Title |
---|
P.C. LANSÅKER等: "TiO2/Au/TiO2 multilayer thin films: Novel metal-based transparent conductors for electrochromic devices", 《THIN SOLID FILMS》 * |
SEIGO ITO等: "Conductive and Transparent Multilayer Films for Low-Temperature-Sintered Mesoporous TiO2 Electrodes of Dye-Sensitized Solar Cells", 《CHEM. MATER.》 * |
Also Published As
Publication number | Publication date |
---|---|
CN112951930B (en) | 2022-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100649838B1 (en) | Transparent conductive laminate and process of producing the same | |
US5977477A (en) | Photovoltaic device | |
US6383345B1 (en) | Method of forming indium tin oxide thin film using magnetron negative ion sputter source | |
CN105821378B (en) | A kind of niobium doping stannic oxide transparent conductive film and preparation method thereof | |
CN101294272A (en) | Method for sputtering and depositing tin indium oxide transparent electroconductive film on flexible substrate at room temperature | |
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 | |
Li et al. | Structure and physical properties evolution of ITO film during amorphous-crystalline transition using a highly effective annealing technique | |
Chiang et al. | Deposition of high-transmittance ITO thin films on polycarbonate substrates for capacitive-touch applications | |
Wen et al. | Room temperature deposition of very thin and flexible crystalline ITO thin film using 3-D facing-magnetron sputtering plasma source | |
Du et al. | Synthesis of high-quality AZO polycrystalline films via target bias radio frequency magnetron sputtering | |
JP2003105533A (en) | Method of producing transparent electroconductive film and transparent electroconductive film | |
Bae et al. | Effects of oxygen ion beam plasma conditions on the properties of Indium tin oxide thin films | |
CN112951930B (en) | Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof | |
WO2008072900A1 (en) | Transparent conductive membrane of high resistance touch panel of capacitance and manufacture method thereof | |
CN102312201A (en) | Preparation method of Al-doped zinc oxide transparent conductive thin film | |
Zhu et al. | Highly transparent conductive F-doped SnO2 films prepared on polymer substrate by radio frequency reactive magnetron sputtering | |
CN108441833B (en) | Multilayer transparent conductive film and preparation method thereof | |
Jung et al. | Process control for low temperature reactive deposition of Al doped ZnO films by ICP-assisted DC magnetron sputtering | |
CN112941479B (en) | Method for adjusting thickness of silver layer by tin dioxide/silver/tin dioxide transparent conductive film and application | |
CN112941476B (en) | Tin dioxide/copper/tin dioxide multilayer transparent conductive film and preparation method and application thereof | |
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 | |
CN108385073B (en) | Method for manufacturing ITO film | |
US20140144770A1 (en) | Method of fabricating zinc oxide thin film |
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 |