CN108130522B - Deposition of TiO on metal surfaces2Method and device for inhibiting micro discharge of thin film - Google Patents

Deposition of TiO on metal surfaces2Method and device for inhibiting micro discharge of thin film Download PDF

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CN108130522B
CN108130522B CN201711405441.XA CN201711405441A CN108130522B CN 108130522 B CN108130522 B CN 108130522B CN 201711405441 A CN201711405441 A CN 201711405441A CN 108130522 B CN108130522 B CN 108130522B
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deposition
tio
deposition substrate
film
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CN108130522A (en
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邵涛
崔超超
王瑞雪
徐晖
任成燕
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Institute of Electrical Engineering of CAS
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process

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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention discloses a method for depositing TiO on the surface of metal under atmospheric pressure2A method of suppressing microdischarges in a thin film, the method comprising: step 1, building an atmospheric pressure plasma jet device; step 2, pre-cleaning the deposition substrate; step 3, TiO is carried out2And (3) thin film deposition: switching on a power supply, and adjusting power supply parameters to enable the jet flow pipe to generate uniform plasma without filaments; adjusting the relative positions of the jet pipe and the deposition substrate to make the jet pipe aligned with the central position of the deposition substrate; the distance between the jet pipe orifice and the deposition substrate is adjusted, so that the substrate cannot be ignited by sparks in the deposition process. The invention has the beneficial effects that: the jet device has a simple structure, can integrate equipment into a portable processor and meets the deposition requirement of a construction site; operations such as annealing and the like are not needed, so that the preparation time is effectively shortened; the production cost is effectively reduced; can realize the TiO treatment on the substrate with irregular surface2And (3) depositing a thin film to meet different industrial requirements.

Description

Deposition of TiO on metal surfaces2Method and device for inhibiting micro discharge of thin film
Technical Field
The invention relates to the technical field of semiconductors, in particular to a method for depositing TiO on a metal surface under atmospheric pressure2A method and apparatus for suppressing micro-discharge in a thin film.
Background
The conductor surfaces of the power transmission line and the high-voltage equipment are easy to have tiny defects, and the local electric field can be seriously distorted due to small curvature radius of the conductor surfaces, so that the local micro-discharge phenomenon is caused. The long-term micro-discharge is easy to cause the damage of insulation, and the safe and stable operation of the power equipment is seriously influenced. At present, the study on the inhibition of partial micro-discharge is mainly developed by scholars at home and abroad from the aspect of insulation. Zhouqia et al fill the gap defect in the cable termination with inorganic nanoparticles to improve the electric field distribution at the gap defect and suppress the damage of the local discharge to the insulation material (Zhouqia, Wu Ke, Wanli et al. effectiveness of inorganic nanoparticles in suppressing the local discharge of the gap defect in the medium voltage cable termination [ J ]. proceedings of electrotechnology, 2016,31 (22): 230-. However, for local micro-discharge caused by micro defects on the metal surface, the situation of electric field distortion cannot be effectively reduced by filling insulating nano particles, and the suppression effect is poor. Starting from the conductor, the micro-protrusion on the surface of the conductor is eliminated, an electric arc aging method is mainly adopted in industry, and the aging result is poor in reliability and controllability.
The semiconductor layer is covered on the surface of the conductor, so that an electric field can be uniform, and the distortion condition of the electric field is improved. TiO22The material is an inorganic semiconductor functional material with wide forbidden band width, has excellent chemical stability, thermal stability, super-hydrophilicity and the like, high photocatalytic activity, excellent electrical characteristics, safety, no toxicity, low cost and no secondary pollution, is widely applied to the fields of photocatalytic catalysts, sensors, dielectric materials, coatings, food packaging materials, self-cleaning glass, aerospace industry and the like, and has very high development and application values. By utilizing the excellent semiconductor characteristics, the cable joint conductor surface is covered with the semiconductor material, so that the electric field distortion caused by the micro-defects on the conductor surface can be effectively weakened, and the aim of inhibiting micro-discharge is fulfilled. However, existing TiO2The preparation method of the film has the advantages of complex and expensive required equipment or complex operation process, long preparation time and incapability of meeting the requirements of the construction site of the power transmission line, so that the research and development of the equipment is simple, the operation is convenient, and the TiO can be quickly and effectively prepared2The thin film method has become a hot point of research.
At present, TiO is studied at home and abroad2The film is prepared by liquid phase method (such as Sol-gel method, liquid phase deposition method, etc.) and gas phase method (such as physical vapor deposition method (PVD)) And Chemical Vapor Deposition (CVD)). The sol-gel method comprises dissolving titanium alkoxide in solvent to obtain sol, coating on substrate, and calcining in muffle furnace to obtain TiO2The method for preparing the film is simple to operate and strong in adaptability, but the precursor of the film is generally titanium alkoxide which is expensive, a large amount of organic solvent is needed in the preparation process, the film preparation cost is high, and the adhesion force between the film and a substrate is poor. The conventional PVD method such as magnetron sputtering and ion beam enhanced deposition requires complicated and expensive equipment and high vacuum requirement. The CVD method using the atmospheric pressure low-temperature plasma assistance has the advantages of simple equipment, convenient operation and strong adaptability, thereby being widely concerned. The patent with application publication number CN 1562463A utilizes the mixed gas of titanium-containing precursor vapor and oxygen-containing or water-containing vapor to directly prepare high-activity supported TiO by the medium barrier discharge plasma with coaxial or plate-plate structure under the conditions of atmospheric pressure and low temperature (room temperature to 300 ℃)2A photocatalyst. The patent with application publication number CN 105755452A reports that the TiO spraying on the inner wall of the tube cavity is realized by using dielectric barrier discharge plasma2The barrier medium of the device is a shapeable hollow dielectric tube, and the device can be designed according to the tube diameter and the bending degree of a tube cavity needing film coating. Due to the limitation of the electrode structure of the dielectric barrier plasma, the object to be processed needs to be placed between the two electrodes, so that strict requirements are imposed on the thickness and the shape of the object to be processed. Li uses Tetraisopropyl Titanate (TTIP) as a precursor, uses a radio frequency power supply to excite plasma dispersion discharge to realize the deposition of a titanium dioxide film, and simultaneously explores the influence of discontinuous growth on the film quality (Li DY, Goullet A, Carette M, et al2films deposited by plasma enhanced chemicalvapour deposition[J]Materials Chemistry and Physics, 2016, 182: 409-417.). KamalBaba uses atmospheric pressure microwave plasma to prepare TiO with compact structure on the surface of the optical fiber by optimizing parameters such as electrode spacing, gas components and the like2Thin films (Kamal Baba, Simon Bulou, Patrick Choquet, et al2Thin Films on Polymer Optical Fiber using Atmospheric-PressurePlasma[J].ACS Applied Materials&Interfaces, 2017, 9 (15): 13733-13741.). The radio frequency and microwave power supply has a complex structure and the problem of power matching exists, so that the production cost is increased.
From the above summary, the current methods for improving the electric field distribution on the surface of the conductor and suppressing the micro-discharge are mainly based on the insulating material, and improve the insulating property and aging property thereof to make the electric field uniform. However, for partial micro-discharge caused by conductor micro-defects, only improving the insulation characteristics cannot effectively weaken the distortion degree of the electric field and inhibit micro-discharge. If the conductor condition is started, the electric field distribution at the defect position is improved, and micro discharge can be fundamentally inhibited. However, few studies on the micro-discharge on the surface of the conductor have been reported. The commonly used electric arc aging in industry has large engineering quantity and poor reliability and controllability.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for depositing TiO on a metal surface2Method and device for inhibiting micro discharge of film, which adopts atmospheric pressure low temperature plasma jet flow auxiliary chemical vapor deposition mode to deposit TiO on the surface of deposition substrate2The film is used for blocking residual gas, and meanwhile, the excellent semiconductor characteristics of the film are utilized to homogenize an electric field, so that the conductor and the surrounding residual air are in a relatively uniform electric field environment, the distortion degree of a local electric field is effectively reduced, micro discharge on the surface of an electrode is effectively inhibited, the insulating capability of the electrode is improved, and the power accident caused by insulation failure is avoided.
The invention provides a metal surface deposited TiO2A method of suppressing microdischarges in a thin film, the method comprising:
step 1, building an atmospheric pressure plasma jet device;
step 2, pre-cleaning the deposition substrate;
step 3, TiO is carried out2And (3) thin film deposition: switching on a power supply, and adjusting power supply parameters to enable the jet flow pipe to generate uniform plasma without filaments; adjusting the relative positions of the jet pipe and the deposition substrate to make the jet pipe aligned with the central position of the deposition substrate; the distance between the jet nozzle and the deposition substrate is adjusted to prevent fire from generating in the deposition processAnd (4) burning the substrate.
As a further improvement of the invention, the specific steps of constructing the atmospheric pressure plasma jet device in the step 1 are as follows:
step 101, connecting a discharge circuit;
102, connecting a high-voltage probe, a current coil and a digital oscilloscope;
and 103, laying a carrier gas, discharge excitation gas and air three-way gas conveying communicating pipeline, checking the air tightness of each gas path, and ensuring that no gas leakage occurs.
As a further improvement of the invention, the step 2 of pre-cleaning the deposition substrate comprises the following specific steps:
step 201, removing an oxide layer on the surface of a deposition substrate, and wiping the oxide layer with deionized water and absolute ethyl alcohol in sequence to remove dust on the surface of the deposition substrate;
202, carrying out ultrasonic cleaning on the deposition substrate in absolute ethyl alcohol and acetone for more than 10min in sequence to remove oil stains and impurities on the surface of the deposition substrate;
and 203, cleaning the deposition substrate again by using deionized water, and drying the deposition substrate in a vacuum drying oven after cleaning to be treated in the next step.
As a further improvement of the invention, the deposited TiO in step 32The power supply of the film is a high-frequency high-voltage alternating current power supply, a high-frequency high-voltage direct current power supply, a microsecond pulse power supply or a nanosecond pulse power supply.
As a further improvement of the invention, the electrode adopted by the atmospheric pressure plasma jet device in the step 1 is a needle-ring electrode, a single needle electrode or a ring-ring electrode.
As a further improvement of the present invention, in step 103, the carrier gas and the discharge excitation gas are all inert gas, air, nitrogen gas or a mixed gas of nitrogen gas and air.
As a further improvement of the invention, the deposition substrate is a conductive metal material with any shape.
The invention also provides a method for depositing TiO on the metal surface2Device for suppressing micro-discharge by thin film, and package thereofComprises the following steps:
the tungsten needle electrode penetrates through the inner quartz tube and is tightly attached to the inner tube wall of the inner quartz tube;
the power supply is connected with a tungsten needle electrode exposed at the upper end of the inner quartz tube;
the outer quartz tube is sleeved outside the inner quartz tube, and the middle part of the outer quartz tube is provided with an air inlet;
the copper ring ground electrode is arranged at the lower part of the outer quartz tube and wraps the outer side of the outer quartz tube; the copper ring ground electrode is grounded through a grounding wire.
The deposition substrate is arranged right below the lower pipe orifice of the outer quartz pipe and is spaced from the lower pipe orifice of the outer quartz pipe;
a thermal stage disposed directly below the deposition substrate and grounded through the ground line;
one end of the bubbler is connected with the gas inlet of the outer quartz tube through a gas conveying pipeline; heating belts are uniformly wound on the connected gas conveying pipelines;
a temperature controller connected to the heating belt;
the first gas cylinder is simultaneously connected with the other end of the bubbler and a gas inlet of the outer quartz tube through gas conveying pipelines respectively;
the second gas cylinder is connected with a gas inlet of the outer quartz tube through a gas conveying pipeline;
and the gas conveying pipeline is provided with a gas mass flow controller.
The invention has the beneficial effects that: the jet device has simple structure, can be carried out under atmospheric pressure, can integrate equipment into a portable processor, and meets the deposition requirement of a construction site; the preparation method is simple to operate, can realize rapid preparation, does not need operations such as annealing and the like, and effectively shortens the preparation time; the used working gas is mainly argon and air with low price, so that the production cost is effectively reduced; can realize the TiO treatment on the substrate with irregular surface2The film is effectively deposited, and different industrial requirements are met.
Drawings
FIG. 1 is a flow chart of TiO2 film deposition on a copper substrate according to an embodiment of the present invention;
FIG. 2 is a schematic view of a jet deposition apparatus according to an embodiment of the present invention;
FIG. 3 shows the chemical composition of a TiO2 thin film according to an embodiment of the invention;
fig. 4 is a graph showing the electric field distribution before and after depositing a TiO2 film according to an embodiment of the present invention.
In the figure, the position of the upper end of the main shaft,
1. a power source; 2. a tungsten needle electrode; 3. an inner quartz tube; 4. an outer quartz tube; 5. grounding; 6. a copper ring ground electrode; 7. depositing a substrate; 8. heating the platform; 9. heating the tape; 10. a temperature controller; 11. a bubbler; 12. a gas mass flow controller; 13. a first gas cylinder; 14. a second gas cylinder.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and with reference to the attached drawings.
As shown in fig. 1, an embodiment of the present invention is a method for suppressing micro-discharge by depositing a TiO2 film on a metal surface, the method comprising:
step 1, building an atmospheric pressure plasma jet device;
step 2, pre-cleaning the deposition substrate;
step 3, TiO is carried out2And (3) thin film deposition: switching on a power supply, and adjusting power supply parameters to enable the jet flow pipe to generate uniform plasma without filaments; adjusting the relative positions of the jet pipe and the deposition substrate to make the jet pipe aligned with the central position of the deposition substrate; the distance between the jet pipe orifice and the deposition substrate is adjusted, so that the substrate cannot be ignited by sparks in the deposition process. Depositing TiO2The film is required to be pretreated on a deposition substrate: firstly, placing a cleaned deposition substrate on a hot table and preheating to 100 ℃; secondly, a temperature controller is arranged to maintain the temperature of the gas channel above 70 ℃ to avoid the condensation of the titanium-containing precursor, wherein the titanium-containing precursor is titanium tetrachloride or tetraisopropyl titanate. Any titanium-containing compound which can easily react with air can be practically used as the titanium-containing compound of the present inventionA precursor; and finally, setting the flow rate of carrier gas to be 20-80sccm, the flow rate of the discharge excitation gas to be 4-6slm and the flow rate of air to be 20-60 sccm. Suitable high voltage power supply equipment and suitable plasma jet generation modes are adopted. Switching on a power supply, adjusting power supply parameters to ensure that uniform plasma is generated in the jet pipe and no filament exists, then moving the heating table and the deposition substrate to be right below the jet plume to ensure that the jet pipe is aligned with the central position of the substrate, adjusting the distance between the nozzle of the jet pipe and the deposition substrate to ensure that the jet plume can be effectively deposited on the deposition substrate and cannot burn the deposition substrate due to the fact that sparks are generated due to too close distance.
Further, the step 1 of establishing the atmospheric pressure plasma jet device comprises the following specific steps:
step 101, connecting a discharge circuit to ensure that all parts of a high-voltage line and a ground wire are in good contact without the phenomena of missing connection and misconnection;
102, connecting a high-voltage probe, a current coil and a digital oscilloscope;
and 103, laying a carrier gas, discharge excitation gas and air three-way gas conveying communicating pipeline, checking the air tightness of each gas path, and ensuring that no gas leakage occurs.
Further, the step 2 of performing a pre-cleaning treatment on the deposition substrate specifically comprises the following steps:
step 201, removing an oxide layer on the surface of a deposition substrate, and wiping the oxide layer with deionized water and absolute ethyl alcohol in sequence to remove dust on the surface of the deposition substrate;
202, carrying out ultrasonic cleaning on the deposition substrate in absolute ethyl alcohol and acetone for more than 10min in sequence to remove oil stains and impurities on the surface of the deposition substrate;
and 203, cleaning the deposition substrate again by using deionized water, and drying the deposition substrate in a vacuum drying oven after cleaning to be treated in the next step.
Further, TiO is deposited in step 32The power supply of the film is a high-frequency high-voltage alternating current power supply, a high-frequency high-voltage direct current power supply, a microsecond pulse power supply or a nanosecond pulse power supply. Any power source can be used as long as it can generate uniform and stable discharge.
Further, the electrode adopted by the atmospheric pressure plasma jet device in the step 1 is a needle-ring electrode, a single needle electrode or a ring-ring electrode.
Further, in step 103, the carrier gas and the discharge excitation gas are inert gas, air, nitrogen gas or a mixed gas of nitrogen gas and air.
Further, the deposition substrate is a conductive metal material with any shape. The deposition substrate can be selected from copper sheets, aluminum sheets or other metal conductive materials. The shape of the deposition substrate can be a sheet, a block or a cylinder, and other irregular surface shapes can also be selected.
As shown in fig. 2, an embodiment of the present invention is an apparatus for suppressing micro-discharge by depositing a TiO2 film on a metal surface, the apparatus comprising:
and the tungsten needle electrode 2 penetrates through the inner quartz tube 3 and is tightly attached to the inner tube wall of the inner quartz tube 3. The tungsten needle electrode 2 in the embodiment of the invention is a high-voltage electrode with the diameter of 2mm and the length of 15 cm.
And the power supply 1 is connected with a tungsten needle electrode 2 exposed at the upper end of the inner quartz tube 3. In the embodiment, the power supply 1 is a high-frequency high-voltage alternating-current power supply, the voltage amplitude is set to be 7-10kV during discharging, and the frequency is set to be 10-60 kHz. In practical application, the parameters are selected based on the ability to generate uniform and stable discharge time.
And the outer quartz tube 4 is sleeved outside the inner quartz tube 3, and the middle part of the outer quartz tube 4 is provided with an air inlet. The outer diameter of the inner quartz tube 3 selected for use in this embodiment is 4mm, the inner diameter is 2mm, and the bottom end is sealed. The outer quartz tube 4 is a T-shaped quartz tube with an outer diameter of 10mm and an inner diameter of 7 mm. The inner quartz tube and the outer quartz tube are coaxially nested and fixed to form a double-medium jet device, and a gap at the upper ends of the inner quartz tube and the outer quartz tube is sealed by sealant.
And the copper ring ground electrode 6 is arranged at the lower part of the outer quartz tube 4 and wraps the outer side of the outer quartz tube 4, and the copper ring ground electrode 6 is grounded through a grounding wire 5. The width of the copper ring ground electrode 6 selected for use in this embodiment is 5 mm. The vertical distance between the tungsten needle electrode 2 and the copper ring ground electrode 6 is 10mm, the distance between the copper ring ground electrode 6 and the lower pipe orifice of the outer quartz tube 4 is 5mm, and during discharging, working gas is introduced from the gas inlet in the middle of the outer quartz tube 4.
A deposition substrate 7 which is arranged right below the lower pipe orifice of the outer quartz tube 4 and has a gap with the lower pipe orifice of the outer quartz tube 4;
and a heat block 8 disposed right under the deposition substrate 7 and grounded through the ground line 5.
In this embodiment, the deposition substrate 7 is a copper sheet with a side length of 4cm and a thickness of 0.05 mm. In the deposition, the copper sheet deposition substrate 7 was placed on a hot stage 8, and the deposition substrate 7 was heated to 100 ℃ by the hot stage 8.
One end of the bubbler 11 is connected with the gas inlet of the outer quartz tube 4 through a gas conveying pipeline; and heating tapes 9 are uniformly wound on the connected gas conveying pipelines. The heating belt 9 is a glass fiber electric heating belt and is uniformly wound on a gas pipeline which is connected with the gas inlet of the outer quartz tube 4 and the bubbler 11. The heating belt 9 heats the gas pipeline connecting the gas inlet of the outer quartz tube 4 and the bubbler 11, and prevents the titanium-containing precursor from condensing on the tube wall of the outer quartz tube 4. The bubbler 11 is an explosion-proof gas bubbling bottle, a proper amount of titanium-containing precursor is filled in the bubbling bottle, and the bubbling bottle is heated to 70 ℃ through water bath, so that the titanium-containing precursor is taken out by carrier gas. In this embodiment, the titanium-containing precursor is titanium tetrachloride and the carrier gas is argon.
And a temperature controller 10 connected to the heating belt 9. The temperature controller 10 is used to control the temperature of the heating belt 9 so that the ventilation pipe of the titanium-containing precursor is maintained at 70 ℃.
And the first gas bottle 13 is connected with the other end of the bubbler 11 and the gas inlet of the outer quartz tube 4 through gas conveying pipelines respectively, and the gas conveying pipelines connected with the first gas bottle are provided with gas mass flow controllers 12. The first gas cylinder 13 is an inert gas cylinder, and the inert gas used in this embodiment is argon. The gas of the first gas bottle 13 is divided into two paths to be output, one path is used as carrier gas, and the gas is introduced into the bubbler 11 to carry out the titanium-containing precursor gas; the other path is used as an electric discharge exciting gas. Both gases are controlled in gas flow rate by gas mass flow controller 12.
And the second gas cylinder 14 is connected with the gas inlet of the outer quartz tube 4 through a gas conveying pipeline, and a gas mass flow controller 12 is arranged on the connected gas conveying pipeline. The second cylinder 14 is an air cylinder that provides oxidizing gas for the reaction during the experiment. This air flow rate is also controlled by the gas mass flow controller 12. And when the three paths of gases are fully mixed, introducing the mixture into a jet reaction device to participate in reaction.
Example 1
Deposition of TiO on copper surfaces by plasma jet2And setting the flow rate of discharge excitation gas argon at 6slm, the flow rate of carrier gas at 60sccm, the flow rate at 40sccm, the discharge voltage at 9kV and the frequency at 50kHz, heating the substrate to 100 ℃ by a hot stage, and carrying out deposition treatment for 2 min. After the completion of the treatment, the composition of the film was analyzed by an X-ray photoelectron spectrometer, and the result is shown in fig. 3 (a). The characteristic peaks of Ti element in the film are a Ti2p3/2 peak at 458.6eV and a Ti2p1/2 peak at 464.3eV, and both are assigned as TiO2Middle Ti4+The reaction product containing Ti element in the film is TiO2. The simulation of the electric field distribution at the micro-defects on the copper surface before and after the deposition of the thin film is shown in FIG. 4. When the processing is not carried out, the field intensity in residual gas at the defect position is larger, and the electric field distortion is serious; after deposition of the film, due to TiO2The film has higher dielectric constant, so that the distortion of an electric field is improved, and the maximum electric field is reduced from 1.4 × 106V/m to 9.89 × 105V/m.
Example 2
Deposition of TiO on copper surfaces by plasma jet2And arranging the flow rates of the discharge excitation gas and the carrier gas to be unchanged, wherein the flow rate is 0sccm, the discharge voltage is 8kV, the frequency is 50kHz, the temperature of the substrate is heated to 100 ℃ by a hot stage, and the deposition treatment is carried out for 2 min. The obtained analysis result of the film component is shown in FIG. 3 (b). The characteristic peak of Ti element in the film is TiO except for 458.6eV and 464.3eV2Middle Ti4+In addition to the characteristic peak of (1), there is a peak at 458.5eV which is ascribed to TiCl4Of Ti4+I.e. when the precursor reaction is incomplete, part of the TiCl4The gas molecules are not decomposed but directly adsorbed in the film.
Example 3
Deposition of TiO on copper surfaces by plasma jet2And the thin film is directly deposited on the surface of the substrate for 2min without heating the substrate, and the flow rate of the placed electric excitation gas and the carrier gas is constant, the air flow rate is 40sccm, the discharge voltage is 9kV, and the frequency is 50 kHz. The obtained analysis result of the film component is shown in FIG. 3 (c). The characteristic peaks of Ti element in the film are represented by Ti at 458.6eV and Ti at 464.3eV4+The characteristic peak is dominant, and the two are attributed to TiO2Middle Ti4+Also present are characteristic peaks at 458.5eV and 459.8eV, both of which are ascribed to TiCl4Of Ti4+. Indicating that the reaction degree of the precursor is lower and more TiCl exists4Adsorbed in the film.
The invention discloses a method for depositing TiO on a metal surface under atmospheric pressure2The method for inhibiting the micro-discharge of the film is to rapidly deposit TiO on the metal surface in situ by utilizing a plasma enhanced chemical vapor deposition method2The film utilizes the semiconductor characteristics of the film to uniform the electric field distribution at the micro-defect position and inhibit micro-discharge. The method is characterized in that: under the conditions of room temperature and atmosphere, a high-voltage power supply is utilized to excite plasma jet discharge, a precursor is activated to carry out gas-phase reaction, and TiO is deposited on the surface of metal2A film. On one hand, the residual gas can be effectively isolated, and the partial discharge caused by the air gap is prevented; on the other hand, TiO2The film has the conductive capacity between the conductor and the insulation, can reduce the electric field distribution gradient between the conductor and the insulation, homogenize the electric field distribution, and reduce the distortion degree of a local electric field so as to inhibit the occurrence of micro-discharge. The method has no special requirements on the shape of the substrate, and can carry out deposition treatment on the material with the special-shaped surface. While for the deposition of SiO on the surface of a conductorxIn the method of suppressing the micro-discharge, the electric field distribution gradient of the insulating film and the conductor is greatly changed, and the conductivity of the conductor may be adversely affected. Deposited SiOxFilm resistivity of about 1011Omega has good insulating property, the forbidden band width is 8.9eV, electrons are difficult to jump from the valence band to the conduction band, and the conductivity is poor. On deposition of SiOxWhen the film is used, the film and the insulation are equipotential, the voltage on the conductor is completely applied to the film, and the electric field intensity is larger. TiO22Is an n-type semiconductor, forbidden bandThe width is 3.0-3.2 eV, and the resistivity decreases with increasing temperature. TiO22Conductivity between conductor and insulator, in comparison with SiOxThe film has good conductivity, so that TiO is deposited2When the film is formed, the potential difference between the other conductors is less than SiOxBetween the film and the conductor, so the electric field intensity is small, and TiO2A certain voltage drop is also formed between the thin film and the insulator, and the electric field distribution is more uniform due to the two-step voltage drop, so that the generation of micro discharge is favorably inhibited.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. Deposition of TiO on metal surfaces2A method for suppressing microdischarges in a thin film, comprising the steps of:
step 1, building an atmospheric pressure plasma jet device;
step 2, pre-cleaning the deposition substrate;
step 3, TiO is carried out2And (3) thin film deposition: switching on a power supply, and adjusting power supply parameters to enable the jet flow pipe to generate uniform plasma without filaments; adjusting the relative positions of the jet pipe and the deposition substrate to make the jet pipe aligned with the central position of the deposition substrate; adjusting the distance between the jet pipe orifice and the deposition substrate to prevent the substrate from being ignited by sparks in the deposition process;
depositing TiO on the metal surface2Metal surface deposited TiO used for method for inhibiting micro discharge by film2The device for inhibiting micro discharge of the film comprises:
the tungsten needle electrode (2) penetrates through the inner quartz tube (3) and is tightly attached to the inner tube wall of the inner quartz tube (3);
the power supply (1) is connected with a tungsten needle electrode (2) exposed at the upper end of the inner quartz tube (3);
the outer quartz tube (4) is sleeved outside the inner quartz tube (3), and an air inlet is formed in the middle of the outer quartz tube (4);
the copper ring ground electrode (6) is arranged at the lower part of the outer quartz tube (4) and wraps the outer side of the outer quartz tube (4); the copper ring ground electrode (6) is grounded through a grounding wire (5);
the deposition substrate (7) is arranged right below the lower pipe orifice of the outer quartz pipe (4) and is spaced from the lower pipe orifice of the outer quartz pipe (4);
a heat block (8) provided directly below the deposition substrate (7) and grounded through the ground line (5);
one end of the bubbler (11) is connected with the gas inlet of the outer quartz tube (4) through a gas conveying pipeline; heating belts (9) are uniformly wound on the connected gas conveying pipelines;
a temperature controller (10) connected to the heating belt (9);
the first gas cylinder (13) is simultaneously connected with the other end of the bubbler (11) and the gas inlet of the outer quartz tube (4) through gas conveying pipelines respectively;
a second gas cylinder (14) connected with the gas inlet of the outer quartz tube (4) through a gas conveying pipeline;
and the gas conveying pipelines are respectively provided with a gas mass flow controller (12).
2. The metal surface deposited TiO of claim 12The method for inhibiting the micro discharge of the film is characterized in that the specific steps of constructing the atmospheric pressure plasma jet device in the step 1 are as follows:
step 101, connecting a discharge circuit;
102, connecting a high-voltage probe, a current coil and a digital oscilloscope;
and 103, laying a carrier gas, discharge excitation gas and air three-way gas conveying communicating pipeline, and checking the air tightness of each gas path.
3. The metal surface deposited TiO of claim 12The method for inhibiting micro discharge of the film is characterized in that the method in step 2The specific steps of pre-cleaning the deposition substrate are as follows:
step 201, removing an oxide layer on the surface of a deposition substrate, and wiping the oxide layer with deionized water and absolute ethyl alcohol in sequence to remove dust on the surface of the deposition substrate;
202, carrying out ultrasonic cleaning on the deposition substrate in absolute ethyl alcohol and acetone for more than 10min in sequence to remove oil stains and impurities on the surface of the deposition substrate;
and 203, cleaning the deposition substrate again by using deionized water, and drying the deposition substrate in a vacuum drying oven after cleaning to be treated in the next step.
4. The metal surface deposited TiO of claim 12The method for inhibiting micro discharge of the film is characterized in that the TiO is deposited in the step 32The power supply of the film is a high-frequency high-voltage alternating current power supply, a high-frequency high-voltage direct current power supply, a microsecond pulse power supply or a nanosecond pulse power supply.
5. The metal surface deposited TiO of claim 12The method for inhibiting the micro discharge by the film is characterized in that the electrode adopted by the atmospheric pressure plasma jet device in the step 1 is a needle-ring electrode, a single needle electrode or a ring-ring electrode.
6. The metal surface deposited TiO of claim 22The method for inhibiting the micro-discharge by the thin film is characterized in that in the step 103, the carrier gas and the discharge excitation gas are inert gas, air, nitrogen or mixed gas of nitrogen and air.
7. The metal surface deposited TiO of claim 12The method for inhibiting the micro discharge of the film is characterized in that the deposition substrate is made of a conductive metal material with any shape.
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