CN108130522A - Metal surface depositing Ti O2Film inhibits the method and device of micro discharge - Google Patents
Metal surface depositing Ti O2Film inhibits the method and device of micro discharge Download PDFInfo
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- CN108130522A CN108130522A CN201711405441.XA CN201711405441A CN108130522A CN 108130522 A CN108130522 A CN 108130522A CN 201711405441 A CN201711405441 A CN 201711405441A CN 108130522 A CN108130522 A CN 108130522A
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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
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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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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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
- C23C16/44—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
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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
- C23C16/44—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
Abstract
The invention discloses metal surface depositing Ti O under a kind of atmospheric pressure2The method that film inhibits micro discharge, this method include：Step 1 builds atmosphere pressure plasma jet flow device；Step 2 carries out prerinse processing to deposition substrate；Step 3 carries out TiO2Thin film deposition：Power on, adjust power parameter, make to generate equably plasma and no filament in jet pipe；The relative position of jet pipe and deposition substrate is adjusted, makes the center of jet pipe alignment deposition substrate；The distance between jet stream nozzle and deposition substrate is adjusted, makes that spark calcination substrate will not be generated in deposition process.Beneficial effects of the present invention are：Fluidic device is simple in structure, can be portable processor by integration of equipments, meets construction site deposition requirement；The operations such as annealing are not needed to, effectively shorten preparation time；Significantly reduce production cost；The TiO to irregular surface substrate can be achieved2Thin film deposition meets different industrial requirements.
Description
Technical field
The present invention relates to technical field of semiconductors, in particular to metal surface depositing Ti O under a kind of atmospheric pressure2It is thin
Film inhibits the method and device of micro discharge.
Background technology
The conductive surface of electric power transmission line and high-tension apparatus is easily there are tiny flaw, due to its radius of curvature very little,
Meeting Severe distortion internal field, so as to cause local micro discharge phenomenon.Long-term micro discharge is easy to cause the destruction of insulation, seriously
Influence the safe and stable operation of power equipment.The research inhibited at present for local micro discharge, domestic and foreign scholars are mainly from insulation
Aspect is unfolded.All triumphant grades are to carrying out inorganic nanoparticles filling at cable termination void defects, so as to improve electric at void defects
Field distribution, inhibiting destruction of the shelf depreciation to insulating materials, (such as Zhou Kai, Wu Ke, ten thousand profit inorganic nanoparticles inhibit midium voltage cable
Validity [J] electrotechnics journals of terminal void defects shelf depreciation, 2016,31 (22)：230-238.).But for metal
Local micro discharge caused by the tiny flaw of surface, filling dielectric nanoparticles cannot effectively reduce electric field distortion situation, inhibit effect
Fruit is poor.And start with from conductor, conductive surface dimpling is eliminated, the industrial main method for using arc conditioning, ageing result can
It is poor by property and controllability.
One semiconductor layer is covered in conductive surface, it can be with uniform electric field so that electric field distortion situation is improved.TiO2
It is a kind of inorganic semiconductor functional material of broad stopband width, there is excellent chemical stability, thermal stability, Superhydrophilic
High Deng, photocatalytic activity, electrology characteristic is excellent, safe and non-toxic, at low cost, non-secondary pollution, has been widely used in photocatalysis
The fields such as catalyst, sensor, dielectric material, coating, packaging material for food, self-cleaning glass, aerospace industry have very high open
Hair and application value.Using its excellent characteristic of semiconductor, cable connector conductive surface is covered in, can effectively weaken conductor
Electric field distortion caused by the microdefect of surface, so as to achieve the purpose that inhibit micro discharge.However, existing TiO2The preparation method of film
Or the operating process of required equipment complex and expensive or needs complexity, preparation time are long, it is impossible to meet transmission line construction scene institute
It needs, therefore, it is simple to research and develop a kind of equipment, easy to operate, can quickly and effectively prepare TiO2The method of film becomes research hotspot.
At present, TiO is studied both at home and abroad2The preparation method of film mainly uses liquid phase method (such as sol-gel method (Sol-
Gel), liquid phase deposition etc.) and vapor phase method (such as physical vaporous deposition (PVD) and chemical vapour deposition technique (CVD)).Colloidal sol-
Gel method is Titanium alkoxides to be dissolved in solvent colloidal sol is made, and is coated on substrate, is roasted with Muffle furnace and TiO is made2The method of film, should
Method is easy to operate, adaptable, but its predecessor is generally expensive Titanium alkoxides, and preparation process needs a large amount of organic
Solvent, film is of high cost, and film and substrate adhesion are poor.Common PVD methods such as magnetron sputtering method, ion beam enhanced depositing
Method, required equipment complex and expensive, vacuum requirement are high.And the CVD method of atmos low-temperature plasma auxiliary is utilized, equipment letter
It is single, it is easy to operate, it is adaptable, thus receive significant attention.The patent that application publication number is 1562463 A of CN utilizes titaniferous
Predecessor steam and oxygen-containing or moisture vapor mixed gas, by same under the conditions of atmospheric pressure and low temperature (room temperature~300 DEG C)
Shaft type or board-to-board formula structural dielectric barrier discharge plasma directly prepare the supported titanium of high activity2Photochemical catalyst.Shen
Please publication No. be CN 105755452 A patent report a kind of realized in tube chamber using dielectric barrier discharge plasma
Wall sprays TiO2The device of nano coating, the block media of the device are the hollow dielectric tube of shaping, and can be according to needing to plate
The caliber and bending degree of membrane tube chamber are designed.It is pending due to the limitation of medium barrier plasma electrode structure itself
Object need to be positioned between two electrodes, therefore treats the thickness of processed material and shape and have strict requirements.D.Li uses metatitanic acid four
Isopropyl ester (TTIP) is discharged using radio-frequency power supply excitation plasma dispersion as predecessor, realizes the heavy of titanium deoxid film
Product, while explore influence (Li D Y, Goullet A, Carette M, et al.Effect of the interruption to film quality
of growth interruptions on TiO2films deposited by plasma enhanced chemical
Vapour deposition [J] .Materials Chemistry and Physics, 2016,182：409-417.).Kamal
Baba uses atmospheric pressure microwave plasma, and structure is made in optical fiber surface by optimizing the parameters such as electrode spacing, gas component
Fine and close TiO2Film (Kamal Baba, Simon Bulou, Patrick Choquet, et al.Photocatalytic
Anatase TiO2Thin Films on Polymer Optical Fiber using Atmospheric-Pressure
Plasma [J] .ACS Applied Materials＆Interfaces, 2017,9 (15)：13733-13741.).Radio frequency and micro-
Wave power supply architecture is complicated, there are problems that power match, makes that the production cost increases.
By above-mentioned summary it is found that improving the distribution of conductive surface electric field at present, inhibiting the method for micro discharge mainly from insulation
Material is started with, and improves its insulation characterisitic and aging characteristics with uniform electric field.And the local micro discharge for caused by conductor microdefect,
Electric field distortion degree cannot effectively be weakened by only improving insulation characterisitic, inhibit micro discharge.If start with from conductor situation, to fault location
Electric field distribution is improved, and can fundamentally inhibit micro discharge.But for the research rare report of conductive surface micro discharge.
Industrial common arc conditioning effect quantities is big, reliability, poor controllability.
Invention content
To solve the above problems, the purpose of the present invention is to provide a kind of metal surface depositing Ti O2Film inhibits micro discharge
Method and device, sunk by the way of atmos low-temperature plasma jet assistant chemical vapor deposition on deposition substrate surface
Product TiO2Film obstructs residual gas, while using its excellent characteristic of semiconductor come uniform electric field so that conductor is residual with surrounding
Remaining air is under more uniform electric field environment, effectively reduces internal field's distortion degree, effectively inhibits electrode surface micro-
Electric discharge so as to improve its insulating capacity, avoids that insulation failure occurs and leads to electric power accident.
The present invention provides a kind of metal surface depositing Ti O2The method that film inhibits micro discharge, this method include：
Step 1 builds atmosphere pressure plasma jet flow device；
Step 2 carries out prerinse processing to deposition substrate；
Step 3 carries out TiO2Thin film deposition：Power on, adjust power parameter, make to generate in jet pipe equably wait from
Daughter and no filament；The relative position of jet pipe and deposition substrate is adjusted, makes the center of jet pipe alignment deposition substrate；
The distance between jet stream nozzle and deposition substrate is adjusted, makes that spark calcination substrate will not be generated in deposition process.
As a further improvement on the present invention, the specific steps of atmosphere pressure plasma jet flow device are built described in step 1
For：
Step 101, connection discharge circuit；
Step 102, connection high-voltage probe, current coil and digital oscilloscope；
Step 103 is laid with three road gas conveying unicom pipeline of carrier gas, discharge excitation gas and air, checks each gas circuit
Air-tightness, it is ensured that without gas leak phenomenon.
As a further improvement on the present invention, described in step 2 to deposition substrate carry out prerinse processing the specific steps are：
Step 201, the oxide layer on removal deposition substrate surface, then successively using deionized water, absolute ethyl alcohol wiping removal
The dust on the deposition substrate surface；
Step 202, successively in absolute ethyl alcohol, acetone to deposition substrate carry out more than ultrasonic cleaning 10min, remove it
The greasy dirt and impurity on surface；
Step 203 cleans deposition substrate using deionized water again, and cleaning is put into vacuum drying chamber after completing
In dried with treat in next step handle.
As a further improvement on the present invention, depositing Ti O described in step 32The power supply of film is high-frequency and high-voltage alternating current
Source, high frequency high voltage dc power source, microsecond pulse power supply or nanosecond pulse power supply.
As a further improvement on the present invention, the electrode that atmosphere pressure plasma jet flow device described in step 1 uses for
Needle-ring electrode, single-needle electrodes or ring-ring electrode.
As a further improvement on the present invention, carrier gas described in step 103, discharge excitation gas are inert gas, sky
The mixed gas of gas, nitrogen or nitrogen and air.
As a further improvement on the present invention, the deposition substrate is the conductive metallic material of arbitrary shape.
The present invention also provides a kind of metal surface depositing Ti O2Film inhibits the device of micro discharge, which includes：
Tungsten needle electrode runs through and is inserted in interior quartz ampoule and is fitted closely with the interior quartz ampoule inner tubal wall；
Power supply is connect with the exposed tungsten needle electrode in the interior quartz ampoule upper end；
Outer quartz ampoule is sleeved on the outside of the interior quartz ampoule, and is equipped with air inlet in the middle part of the outer quartz ampoule；
Copper ring ground electrode is set on the lower part of the outer quartz ampoule and is wrapped in the outside of the outer quartz ampoule；The copper
Ring ground electrode passes through ground connection.
Deposition substrate is set on the underface of the outer quartz ampoule lower nozzle and between the outer quartz ampoule lower nozzle presence
Every；
Thermal station is set on the underface of the deposition substrate and passes through the ground connection；
Bubbler, one end are connect by gas transmission pipeline with the air inlet of the outer quartz ampoule；And in the gas of connection
Heating tape is uniformly tied on body conveyance conduit；
Temperature controller, with the heating band connection；
First gas cylinder, respectively by gas transmission pipeline simultaneously with the bubbler other end, the outer quartz ampoule
Air inlet connects；
Second gas cylinder is connect by gas transmission pipeline with the air inlet of the outer quartz ampoule；
The gas transmission pipeline is equipped with gas mass flow controller.
Beneficial effects of the present invention are：This method fluidic device is simple in structure, can carry out under atmospheric pressure, can be by equipment
Portable processor is integrated into, meets construction site deposition requirement；It is easy to operate, it can be achieved that quick prepare, do not need to annealing etc.
Operation, effectively shortens preparation time；And the working gas used is mainly cheap argon gas and air, is effectively dropped
Low production cost；The TiO to irregular surface substrate can be achieved2Film effectively deposits, and meets different industrial requirements.
Description of the drawings
Fig. 1 is the copper-based bottom sediments TiO2 film flow charts described in the embodiment of the present invention；
Fig. 2 is the jet stream precipitation equipment schematic diagram described in the embodiment of the present invention；
Fig. 3 is the TiO2 film chemicals composition described in the embodiment of the present invention；
Fig. 4 is the distribution map of the electric field before and after the depositing Ti O2 films described in the embodiment of the present invention.
In figure,
1st, power supply；2nd, tungsten needle electrode；3rd, interior quartz ampoule；4th, outer quartz ampoule；5th, it is grounded；6th, copper ring ground electrode；7th, base is deposited
Bottom；8th, thermal station；9th, heating tape；10th, temperature controller；11st, bubbler；12nd, gas mass flow controller；13rd, the first gas cylinder；
14th, the second gas cylinder.
Specific embodiment
The present invention is described in further detail below by specific embodiment and with reference to attached drawing.
As shown in Figure 1, described in the embodiment of the present invention being a kind of side that metal surface depositing Ti O2 films inhibit micro discharge
Method, this method include：
Step 1 builds atmosphere pressure plasma jet flow device；
Step 2 carries out prerinse processing to deposition substrate；
Step 3 carries out TiO2Thin film deposition：Power on, adjust power parameter, make to generate in jet pipe equably wait from
Daughter and no filament；The relative position of jet pipe and deposition substrate is adjusted, makes the center of jet pipe alignment deposition substrate；
The distance between jet stream nozzle and deposition substrate is adjusted, makes that spark calcination substrate will not be generated in deposition process.Depositing Ti O2Film
It needs to pre-process deposition substrate before：First, cleaned deposition substrate is placed in thermal station and is preheated to 100
℃；Secondly, set temperature controller makes gas passage temperature maintain 70 DEG C or more and avoids condensing containing titanium precursor, this implementation
It is titanium tetrachloride or tetraisopropyl titanate to contain titanium precursor in example.As long as in practical applications can easily with air reaction
Titanium-containing compound can contain titanium precursor as the present patent application；Finally, setting flow rate of carrier gas is 20-80sccm, is discharged
The flow velocity of excited gas is 4-6slm, air velocity 20-60sccm.Using suitable high-voltage power-supply unit and it is suitable wait from
Daughter jet stream producing method.Power on, adjust power parameter, it is ensured that equably plasma is generated in jet pipe and without thin
Then thermal station and deposition substrate are moved to immediately below jet stream plumage by silk, it is ensured that jet pipe alignment base center position adjusts jet stream
The distance between nozzle and deposition substrate, it is ensured that jet stream plumage can be deposited effectively and will not be because of the too near production of distance on the deposition substrate
It lights a fire and spends and calcination deposition substrate.
Further, step 1 build atmosphere pressure plasma jet flow device the specific steps are：
Step 101, connection discharge circuit, make high-tension line and ground wire contact everywhere well, nothing is missed, misconnection phenomenon；
Step 102, connection high-voltage probe, current coil and digital oscilloscope；
Step 103 is laid with three road gas conveying unicom pipeline of carrier gas, discharge excitation gas and air, checks each gas circuit
Air-tightness, it is ensured that without gas leak phenomenon.
Further, step 2 to deposition substrate carry out prerinse processing the specific steps are：
Step 201, the oxide layer on removal deposition substrate surface, then successively using deionized water, absolute ethyl alcohol wiping removal
The dust on deposition substrate surface；
Step 202, successively in absolute ethyl alcohol, acetone to deposition substrate carry out more than ultrasonic cleaning 10min, remove it
The greasy dirt and impurity on surface；
Step 203 cleans deposition substrate using deionized water again, and cleaning is put into vacuum drying chamber after completing
In dried with treat in next step handle.
Further, depositing Ti O in step 32The power supply of film is high frequency and high voltage power supply, high-frequency high-voltage direct-current electricity
Source, microsecond pulse power supply or nanosecond pulse power supply.As long as uniform and stable electric discharge can be generated, it can be used as the present patent application
In power supply.
Further, the electrode that atmosphere pressure plasma jet flow device uses in step 1 is needle-ring electrode, single-needle electrodes
Or ring-ring electrode.
Further, carrier gas, discharge excitation gas are inert gas, air, nitrogen or nitrogen and air in step 103
Mixed gas.
Further, deposition substrate is the conductive metallic material of arbitrary shape.Deposition substrate can be selected copper sheet, aluminium flake or
Other conductive metal materials.The shape of deposition substrate can be sheet, bulk or cylinder, other can also be selected irregular
The shape on surface.
As shown in Fig. 2, described in the embodiment of the present invention being a kind of dress that metal surface depositing Ti O2 films inhibit micro discharge
It puts, which includes：
Tungsten needle electrode 2 runs through and is inserted in interior quartz ampoule 3 and is fitted closely with interior 3 inner tubal wall of quartz ampoule.The present invention is implemented
The selection of tungsten needle electrode 2 in example is high-field electrode, a diameter of 2mm, a length of 15cm.
Power supply 1 is connect with the exposed tungsten needle electrode 2 in interior 3 upper end of quartz ampoule.Power supply 1, which is selected, in the present embodiment is
High frequency and high voltage power supply, voltage magnitude is set as 7-10kV, set of frequency 10-60kHz during electric discharge.Join in practical applications
Number is selected can generate discharge time that is uniform, stablizing as foundation.
Outer quartz ampoule 4, set is in the outside of interior quartz ampoule 3, and 4 middle part of outer quartz ampoule is equipped with air inlet.In the present embodiment
The outer diameter for the interior quartz ampoule 3 selected is 4mm, and internal diameter 2mm, bottom end is sealed.Outer quartz ampoule 4 is T-shaped quartz ampoule, and outer diameter is
10mm, internal diameter 7mm.The fluidic device of the coaxial nested fixed double media of composition of inside and outside quartz ampoule, inside and outside quartz ampoule upper end gap
It is sealed by fluid sealant.
Copper ring ground electrode 6 is set on the lower part of outer quartz ampoule 4 and is wrapped in the outside of outer quartz ampoule 4, copper ring ground electrode 6
Pass through 5 ground connection of ground wire.6 width of copper ring ground electrode that the present embodiment is selected is the patch copper foil of 5mm.Tungsten needle electrode 2 and copper ring
Vertical range between ground electrode 6 is 10mm, and the distance of copper ring ground electrode 6 and the lower nozzle of outer quartz ampoule 4 is 5mm, during electric discharge,
Working gas is passed through by the air inlet at outer 4 middle part of quartz ampoule.
Deposition substrate 7 is set on the underface of outer 4 lower nozzle of quartz ampoule and there is interval with outer 4 lower nozzle of quartz ampoule；
Thermal station 8 is set on the underface of deposition substrate 7 and passes through 5 ground connection of ground wire.
It is 4cm that the selection of deposition substrate 7, which is the length of side, in the present embodiment, and thickness is the copper sheet of 0.05mm.When being deposited,
The copper sheet deposition substrate 7 is placed in thermal station 8, deposition substrate 7 is heated to 100 DEG C by thermal station 8.
Bubbler 11, one end are connect by gas transmission pipeline with the air inlet of outer quartz ampoule 4；And in the gas of connection
Heating tape 9 is uniformly tied on conveyance conduit.Heating tape 9 is glass fibre ribbon heater, and uniform winding is in the air inlet of outer quartz ampoule 4
On the gas pipeline being connect with bubbler 11.9 external 4 air inlet of quartz ampoule of heating tape and the gas pipeline that bubbler 11 is connect into
Row heating, prevents from condensing on the tube wall of outer quartz ampoule 4 containing titanium precursor.Bubbler 11 is anti-explosion type gas bubbling bottle,
Equipped in right amount containing titanium precursor, and pass through heating water bath to 70 DEG C in bottle, make carrier gas that will contain titanium precursor and take out of.In the present embodiment
It is titanium tetrachloride containing titanium precursor to select, and gas of carrier gas is argon gas.
Temperature controller 10 is connect with heating tape 9.Temperature controller 10 is with in the temperature of control heating tape 9, making to contain
The ventilation pipe of titanium precursor maintains 70 DEG C.
First gas cylinder 13, the respectively air inlet with bubbler 11 other end, outer quartz ampoule 4 simultaneously by gas transmission pipeline
Mouth connection, and it is equipped with gas mass flow controller 12 on the gas transmission pipeline connected.First gas cylinder 13 is inert gas
Gas cylinder, the inert gas selected in the present embodiment are argon gas.The gas of first gas cylinder 13 is divided into two-way output, all the way as load
Gas, gas are passed through in bubbler 11 and take titaniferous precursor gas out of；Another way is as discharge excitation gas.The two-way gas is equal
Its gas flow rate is controlled by gas mass flow controller 12.
Second gas cylinder 14 is connect by gas transmission pipeline with the air inlet of outer quartz ampoule 4, and the gas conveying connected
Pipeline is equipped with gas mass flow controller 12.Second gas cylinder 14 is air gas cylinder, provides oxygen for reaction during the experiment
Change gas.The air velocity is controlled also by gas mass flow controller 12.It is passed through after three road gases are sufficiently mixed
Reaction is participated in jet reaction device.
Embodiment 1
Using plasma jet in copper surface depositing Ti O2Film, setting discharge excitation gases argon flow velocity are 6slm,
Flow rate of carrier gas is 60sccm, air velocity 40sccm, discharge voltage 9kV, frequency 50kHz, and thermal station heats base reservoir temperature to 100
DEG C, deposition processes 2min.Thin film composition is analyzed using x-ray photoelectron spectroscopy after the completion of processing, result such as Fig. 3
(a) shown in.Ti elemental characteristics peak is the Ti2p3/2 peaks at 458.6eV and the Ti2p1/2 peaks at 464.3eV in film, both
It is attributed to TiO2Middle Ti4+, the reaction product for showing the element containing Ti in film is TiO2.Copper surface field at micro-defect before and after thin film deposition
Electric field distributed simulation situation is as shown in Figure 4.When untreated, field strength is larger in fault location residual gas, and electric field distortion is serious；Deposition
After film, due to TiO2Film has higher dielectric constant so that electric field distortion situation is improved, maximum field by 1.4 ×
106V/m drops to 9.89 × 105V/m.
Embodiment 2
Using plasma jet in copper surface depositing Ti O2Film sets discharge excitation gas and flow rate of carrier gas not
Become, air velocity 0sccm, discharge voltage 8kV, frequency 50kHz, thermal station heats base reservoir temperature to 100 DEG C, deposition processes
2min.Shown in obtained thin film composition analysis result such as Fig. 3 (b).In film Ti elemental characteristics peak in addition to 458.6eV and
TiO is attributed at 464.3eV two2Middle Ti4+Characteristic peak outside, also exist be located at 458.5eV at peak, this feature peak is attributed to
TiCl4In Ti4+, i.e. predecessor reaction at this time is incomplete, part TiCl4Gas molecule is not decomposed but directly adsorbs in thin
In film.
Embodiment 3
Using plasma jet in copper surface depositing Ti O2Film sets discharge excitation gas and flow rate of carrier gas not
Become, air velocity 40sccm, discharge voltage 9kV, frequency 50kHz do not heat substrate, directly heavy on its surface
Product processing 2min.Shown in obtained thin film composition analysis result such as Fig. 3 (c).In film Ti elemental characteristics peak with 458.6eV and
464.3eV the Ti at place4+Based on characteristic peak, the two is attributed to TiO2Middle Ti4+, while also exist and be located at 458.5eV and 459.8eV
Characteristic peak, the two is all attributed to TiCl4In Ti4+.Show that the predecessor extent of reaction is relatively low at this time, there is more TiCl4It inhales
It is attached in the film.
Disclosed by the invention is depositing Ti O in metal surface under a kind of atmospheric pressure2The method that film inhibits micro discharge, that is, utilize
The method of plasma enhanced chemical vapor deposition, in metal surface quick in situ depositing Ti O2Film utilizes partly leading for film
Bulk properties, uniform field at micro-defect electric field distribution, inhibits micro discharge.It is characterized in that：Under room temperature, atmospheric conditions, high-voltage electricity is utilized
Source excitation plasma jet discharges, and gas phase reaction occurs for activation predecessor, in metal surface depositing Ti O2Film.It on the one hand can
Effectively to completely cut off residual gas, prevent news because air gap due to shelf depreciation occurs；On the other hand, TiO2Thin film conductive ability is situated between
Between conductor and insulation, electric field distribution gradient between conductor and insulation can be reduced, uniform electric field distribution reduces internal field
Distortion degree, to inhibit the generation of micro discharge.This method to shapes of substrates without particular/special requirement, can to the material of compromise face into
Row deposition processes.And for depositing SiO using in conductive surfacexTo inhibit the method for micro discharge, insulation film and conductor electricity
Field distribution graded is larger, may have an adverse effect to the electric conductivity of conductor.The SiO of depositionxFilm resiativity is about
1011Ω, insulation performance is preferable, energy gap 8.9eV, and electronics is difficult to transit to conduction band from valence band, thus its electric conductivity is very
Difference.In deposition SiOxDuring film, with insulation equipotential, the voltage on conductor is all applied on film film, electric field strength compared with
Greatly.TiO2It is a kind of n-type semiconductor, energy gap is 3.0eV~3.2eV, and resistivity is increased with temperature and reduced.TiO2It leads
Electrically between conductor and insulator, compare SiOxFilm conductivity is good, thus depositing Ti O2During film, between remaining conductor
Potential difference is less than SiOxBetween film and conductor, so electric field strength is smaller, while TiO2Also have one between film and insulator
Fixed voltage drop, the ladder twice of voltage lands so that electric field distribution is more uniform, so being conducive to inhibit the generation of micro discharge.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. metal surface depositing Ti O2The method that film inhibits micro discharge, which is characterized in that include the following steps：
Step 1 builds atmosphere pressure plasma jet flow device；
Step 2 carries out prerinse processing to deposition substrate；
Step 3 carries out TiO2Thin film deposition：Power on, adjust power parameter, make to generate equably plasma in jet pipe
And without filament；The relative position of jet pipe and deposition substrate is adjusted, makes the center of jet pipe alignment deposition substrate；Adjustment
Distance between jet stream nozzle and deposition substrate makes that spark calcination substrate will not be generated in deposition process.
2. depositing Ti O in metal surface according to claim 12The method that film inhibits micro discharge, which is characterized in that step 1
It is described build atmosphere pressure plasma jet flow device the specific steps are：
Step 101, connection discharge circuit；
Step 102, connection high-voltage probe, current coil and digital oscilloscope；
Step 103 is laid with three road gas conveying unicom pipeline of carrier gas, discharge excitation gas and air, and checks each gas circuit
Air-tightness.
3. depositing Ti O in metal surface according to claim 12The method that film inhibits micro discharge, which is characterized in that step 2
It is described to deposition substrate carry out prerinse processing the specific steps are：
Step 201, the oxide layer on removal deposition substrate surface, then successively using described in deionized water, absolute ethyl alcohol wiping removal
The dust on deposition substrate surface；
Step 202, successively in absolute ethyl alcohol, acetone to deposition substrate carry out more than ultrasonic cleaning 10min, remove its surface
Greasy dirt and impurity；
Step 203 cleans deposition substrate using deionized water again, cleaning complete after be put into vacuum drying chamber into
Row dries to treat to handle in next step.
4. depositing Ti O in metal surface according to claim 12The method that film inhibits micro discharge, which is characterized in that step 3
Described in depositing Ti O2The power supply of film is high frequency and high voltage power supply, high frequency high voltage dc power source, microsecond pulse power supply or receives
Pulse per second (PPS) power supply.
5. depositing Ti O in metal surface according to claim 12The method that film inhibits micro discharge, which is characterized in that step 1
Described in the electrode that uses of atmosphere pressure plasma jet flow device for needle-ring electrode, single-needle electrodes or ring-ring electrode.
6. depositing Ti O in metal surface according to claim 22The method that film inhibits micro discharge, which is characterized in that step
Carrier gas described in 103, discharge excitation gas are the mixed gas of inert gas, air, nitrogen or nitrogen and air.
7. depositing Ti O in metal surface according to claim 12The method that film inhibits micro discharge, which is characterized in that described
Deposition substrate is the conductive metallic material of arbitrary shape.
8. a kind of metal surface depositing Ti O2Film inhibits the device of micro discharge, which is characterized in that including：
Tungsten needle electrode (2) runs through and is inserted in interior quartz ampoule (3) and is fitted closely with interior quartz ampoule (3) inner tubal wall；
Power supply (1) is connect with the exposed tungsten needle electrode (2) in interior quartz ampoule (3) upper end；
Outer quartz ampoule (4) is sleeved on the outside of the interior quartz ampoule (3), and air inlet is equipped in the middle part of the outer quartz ampoule (4)；
Copper ring ground electrode (6) is set on the lower part of the outer quartz ampoule (4) and is wrapped in the outside of the outer quartz ampoule (4)；Institute
It states copper ring ground electrode (6) and is grounded by being grounded (5)；
Deposition substrate (7), be set on outer quartz ampoule (4) lower nozzle underface and with outer quartz ampoule (4) lower nozzle
There are intervals；
Thermal station (8) is set on the underface of the deposition substrate (7) and passes through ground wire (5) ground connection；
Bubbler (11), one end are connect by gas transmission pipeline with the air inlet of the outer quartz ampoule (4)；And in connection
Heating tape (9) is uniformly tied on gas transmission pipeline；
Temperature controller (10) is connect with the heating tape (9)；
First gas cylinder (13), respectively by gas transmission pipeline simultaneously with the bubbler (11) other end, the outer quartz
Manage the air inlet connection of (4)；
Second gas cylinder (14) is connect by gas transmission pipeline with the air inlet of the outer quartz ampoule (4)；
Gas mass flow controller (12) is respectively equipped on the gas transmission pipeline.
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