CN102011102A - Normal-temperature deposition equipment for high-interfacial strength diamond film materials and method thereof - Google Patents
Normal-temperature deposition equipment for high-interfacial strength diamond film materials and method thereof Download PDFInfo
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Abstract
The invention relates to normal-temperature deposition equipment for high-interfacial strength diamond film materials and a method thereof. The equipment adopts a composite anode consisting of a planar plate electrode and a tungsten wire coil electrode; an acute angled triangular notch is machined on the tungsten wire coil anode to form a point discharge point; and in direct current (DC) plasma discharge, a microporous structure with a certain density is formed on the surface of a diamond like carbon (DLC) film so as to make the DLC film become a discontinuous film, and the compressed residual stress in the film is reduced. By ascending and descending the composite anode, the density of micropores formed on the surface of the DLC film can be controlled. A power supply is a DC-radio frequency (RF) dual-power supply system, a direct current (DC) plasma generating source makes a coating and the film have high bond strength and also makes the coating and a metal matrix have higher bond strength. A dense DLC film structure is formed by a radio frequency (RF) method, and the abrasion resistance of the film is improved. Meanwhile, the tungsten wire coil electrode is converted into a hot filament, the hot filament-assisted chemical vapor deposition (CVD) process is formed, and the deposition speed of the film is improved. The deposition equipment is long in service life and contributes to popularization and implementation.
Description
Technical field
The present invention relates to a kind of deposition method and equipment of DLC diamond like carbon film material, particularly relate to the normal temperature depositing device and the normal temperature deposition method thereof of the discontinuous surperficial diamond like carbon film material of a kind of high interfacial bonding strength porous.
Background technology
Diamond like carbon film (Diamond-like Carbon Films is called for short the DLC film) is that characteristics such as a class hardness, optics, electricity, chemistry and tribology all are similar to adamantine amorphous carbon-film.For example, it has characteristics such as high rigidity, friction resistant, unreactiveness, low-k, wide optical band gap, excellent biological compatibility.It can be applied to fields such as machinery, electronics, chemistry, military affairs, aerospace, has broad application prospects.
At present, the method for preparing the DLC diamond like carbon film mainly comprises physical vapor deposition and chemical vapour deposition, for example ion beam depositing, cathode arc deposition, sputtering sedimentation and plasma enhanced chemical vapor deposition etc.Though most methods wherein can deposit quality diamond like carbon film preferably, but the complicacy of gas phase compound experiment device and the high temperature of substrate have all caused these methods to have certain limitation, have limited the practical application of DLC diamond like carbon film to a certain extent.
Quasi-diamond (DLC) thin-film material is a most representative class material in low friction solid lubrication high-abrasive material, has realized industrialization the nineties abroad.But in order to widen its range of application, need further to improve its boundary strength, how can further improve its boundary strength is the technology emphasis of various countries' research.Now developed multiple middle transition dielectric material technology, be configured with: Si+DLC, soaked carbon+Cr+DLC, Cr/W+DLC and atom injects nitriding treatment+DLC etc. as handling the DLC diamond like carbon film for the compound surface of mechanical component.Along with continuous technological development and research, its manufacture method also constantly increases, for example: the improvement of PVD physical vaporous deposition technology, can produce no hydrogen DLC diamond like carbon film, and be successfully used to the manufacturing of motor car engine piston ring and connecting bar and crankshaft.Domestic present DLC diamond like carbon film material also is in conceptual phase, do not have the industrialization production technology, but have many units also energetically research and development in, inspire confidence in company, Jilin University, the world, Beijing Diamant Boart Inc. etc. as University of Science ﹠ Technology, Beijing, Shanghai Communications University, Guangdong non-ferrous metal research institute, Shengli Oil Field Dongying enlightening.
At present, the key issue that exists for DLC diamond like carbon film material manufacturing technology aspect is the boundary strength problem that do not solve well, can't practical application thereby cause.It is reported that recently University of Science ﹠ Technology, Beijing gives processing and solved the boundary strength problem by being coated with boron.Boride, silicon, metallic carbide, metal nitride etc. can both solve the interface problem of DLC diamond like carbon film as intermediate layer in fact, but apply and expensive and producing apparatus complicated that sedimentary two procedures will cause the DLC diamond like carbon film, the process that is easy to generate is simultaneously polluted, and the processing of complex construction component (concaveconvex structure) is also had sizable difficulty.
Patent documentation report about DLC diamond like carbon film material preparation aspect also has many, for example: 1, application number is that 200910066757.X, denomination of invention are the patent of invention of " a kind of method of diamond like carbon film of low temperature depositing changeable refractive index ", and this patent of invention adopts existing vacuum chamber and Process configuration; At room temperature, regulate substrate to the distance that has between the grid Kaufman ion source; The vacuum tightness of regulating vacuum chamber reaches 2 * 10
-3The Pa magnitude; Select CH
4And H
2As precursor gases, in 4: 1 ratio, be transported in the grid Kaufman ion source, before the deposition beginning, in substrate, apply earlier-negative bias of 20V; After the deposition beginning, the vacuum tightness of vacuum chamber remains on 1 * 10
-2The Pa magnitude, it is 120mA that control has the ionogenic discharging current of grid Kaufman.Ion beam energy can be a diamond like carbon film between the 1.7-2.3 obtaining specific refractory power in the substrate when 100eV-600eV.2, application number is 200810103011.7, denomination of invention is the patent of invention of " a kind of method of preparing diamond-like film by low voltage liquid phase electrodeposit ", this patent of invention is negative electrode with the indium tin oxide-coated glass, platinized platinum is an anode, methane amide is an electrolytic solution, under normal temperature condition, by between negative and positive two electrodes, applying the volts DS of 3～30V, can on the indium tin oxide-coated glass negative electrode, deposit diamond like carbon film.This method has that equipment is simple, energy consumption is low, sedimentation rate reaches advantages such as the film forming homogeneity is good soon, is easy to realize suitability for industrialized production.3, application number is 200810110529.3, denomination of invention is the patent of invention of " a kind of deposition methods of TiC/DLC multilayer film ", and this patent of invention adopts magnetic to filter titanium arc source depositing Ti layer; Adopt pulse graphite arc source deposition DLC layer; Adopt magnetic to filter titanium arc source and pulse graphite arc source common deposited TiC layer, control Ti content in the TiC layer by the pulse-repetition in regulating impulse graphite arc source.Adopt the internal stress of the sedimentary TiC/DLC multilayer film of arc ion plating (aip) internal stress less than the quasi-diamond single thin film, the performance characteristics that has kept diamond like carbon film high rigidity and low-friction coefficient simultaneously, sedimentary TiC/DLC multilayer film total thickness can reach 2 μ m, and has excellent abrasion resistance properties.
Summary of the invention
The technical problem to be solved in the present invention is: normal temperature depositing device and normal temperature deposition method thereof that the discontinuous surperficial diamond like carbon film material of a kind of high interfacial bonding strength porous is provided.The crucial difficult problem that can solve the existence of DLC diamond like carbon film material manufacturing technology aspect by technical solution of the present invention is the boundary strength problem.Utilize technical solution of the present invention to prepare DLC diamond like carbon film material, can solve the film inner high voltage residual stress problems that contracts well, thereby prepare the discontinuous surperficial diamond like carbon film material of the porous with high interfacial bonding strength.
In order to address the above problem, the technical solution used in the present invention is:
The invention provides a kind of normal temperature depositing device of high interfacial strength diamond like carbon film material, contain the sediment chamber, be communicated with unstripped gas intake ducting and vacuum extractor with the sediment chamber, be provided with the negative electrode Stage microscope that is connected with the plasma generating source negative pole at sediment chamber's inner bottom part, be provided with and the anodal anode that is connected of plasma generating source at the deposition chamber interior upside, wherein anode is electrically connected with the sediment chamber, the sediment chamber is connected with ground wire, and heat filament device, described anode is a composite anode, this composite anode comprises a dull and stereotyped anode and a refractory metal wire coil anode, its middle plateform anode is positioned at refractory metal wire coil anode upside, and dull and stereotyped anode all is connected with the plasma generating source anode with refractory metal wire coil anode; Described plasma generating source is that source and an alternation plasma generating source take place a DC direct current plasma, and the positive pole of two plasma generating sources is connected with sediment chamber's shell, and the negative electrode of two plasma generating sources is connected with negative electrode by cutting off switch respectively.The fusing point of refractory metal wire coil described herein is not less than 1800 ℃.
On described refractory metal silk surface, certain distance offers the triangular notch of band acute angle at interval, and the point of this acute angle is not less than the par, constitutes the point discharge point.
Described refractory metal wire coil anode is the tungsten filament coil anode, perhaps is molybdenum filament coil anode, perhaps is tantalum wire coil anode, and perhaps other fusing points are not less than 1800 ℃ wire coils anode.
Described heat filament device comprises refractory metal wire coil, the direct supply that is used to heat and grounding switch, the two ends of this refractory metal wire coil are connected with the positive and negative electrode of the direct supply that is used to heat respectively, and the supply lead of this refractory metal wire coil keeps break-make by a grounding switch and sediment chamber's shell, and the partition switch is installed on the output terminal of the direct supply that is used to heat simultaneously.
Described alternation plasma generating source is that the source takes place the RF radio frequency plasma, perhaps for the DC pulse plasma source takes place or for high frequency plasma generation source or be microwave plasma generation source, perhaps other alternation plasma generating sources.
Insulate by vitrified pipe between described dull and stereotyped anode and the refractory metal wire coil anode, directly conducting, thus dull and stereotyped anode and refractory metal wire coil anode are fixed as one; Upside in the sediment chamber also is equipped with a riser that is used for distance between composite anode and the negative electrode, thereby makes composite anode move up and down the distance of adjusting between composite anode and the negative electrode by adjusting riser.
About composite anode, the change aspect electrode geometry stands good, for example combined electrode of being constituted of cylindrical anode and cylindrical tungsten filament coil electrode etc.
Vacuum extractor adopts the two-stage vacuum system, and main vacuum pump adopts molecular pump or diffusion pump, and secondary pump adopts rotary-vane vaccum pump.
A kind of method of utilizing above-mentioned normal temperature depositing device normal temperature deposition high interfacial strength diamond like carbon film material said method comprising the steps of:
A, at first adjust the distance between the composite anode and negative electrode in the above-mentioned depositing device, on the negative electrode Stage microscope, place base material then, utilize the vacuum extractor that is communicated with the sediment chamber that the vacuum pressure in the sediment chamber is evacuated to and be not less than 5 * 10
-3Pa;
B, then the DC direct current plasma generation source in the depositing device is closed, and by cutting off the disconnection of switch and equipment, open the Ar source of the gas air intake valve that is communicated with the sediment chamber, feed Ar gas, adjust vacuum pressure to the 10～12Pa in the sediment chamber, sediment chamber's internal pressure reaches that the flow of Ar gas remains unchanged behind 10～12Pa, open the direct supply and the alternation plasma generating source that are used to heat in the heat filament device, adopt conventional heated filament assisted CVD method that base material is carried out 8～15 minutes plasma bombardment, remove the pollutent of substrate surface;
The deposition process of c, a-Si:H:C intermediate layer: close the direct supply and the alternation plasma generating source that are used to heat in Ar source of the gas air intake valve, the heat filament device then, disconnect by cutting off switch and equipment respectively, open tetramrthylsilane (CH then
3)
4The gas source air intake valve feeds tetramrthylsilane (CH
3)
4Gas is adjusted vacuum pressure to the 15～17Pa in the sediment chamber, and sediment chamber's internal pressure reaches Si (CH behind 15～17Pa
3)
4The flow of gas remains unchanged, and the source takes place the DC direct current plasma of opening in the depositing device, between refractory metal wire coil anode and base material plasma discharge takes place, deposition a-Si:H:C middle transition layer film 18～22 minutes;
The deposition process of d, DLC diamond like carbon film material: after the thin film deposition of a-Si:H:C intermediate layer, reduce Si (CH gradually
3)
4The flow of gas is opened hydrocarbon gas and H simultaneously
2The air intake valve of gas imports hydrocarbon gas and H
2Gas, hydrocarbon gas and H
2The flow proportional of gas between the two is 1:4, Si (CH after 10～15 minutes
3)
4The flow of gas is reduced to zero, and this moment, the air intake valve of tetramethylsilane gas source was closed fully, by the air inlet needle-valve flow of hydrocarbon gas is adjusted to 5sccm, H
2The flow of gas is adjusted to 20sccm, and the vacuum pressure in the sediment chamber remains on 25Pa, deposition DLC diamond like carbon film bottom 15～18 minutes; Then DC direct current plasma generation source is closed, disconnected by cutting off switch and equipment;
E, open the direct supply that is used to heat in the heat filament device then, feed electric current to refractory metal wire coil anode, open the alternation plasma generating source, the hydrocarbon gas flow in this moment sediment chamber still keeps 5sccm, H
2Gas flow keeps 20sccm, vacuum pressure in the sediment chamber is 25Pa, deposition DLC thin film layer 42～45 minutes, obtain the diamond like carbon film of composite structure after the deposition, orderly close-down alternation plasma generating source and the direct supply that is used to heat then, disconnect by cutting off switch and equipment respectively, and close hydrocarbon gas source and H
2The air intake valve of gas source obtains the discontinuous surperficial diamond like carbon film material of porous of product high interfacial bonding strength of the present invention at last.
According to the method for above-mentioned normal temperature deposition high interfacial strength diamond like carbon film material, the distance between composite anode described in the step a and the negative electrode is 30～60mm.
According to the method for above-mentioned normal temperature deposition high interfacial strength diamond like carbon film material, the rf bias of the plasma generating source of alternation described in the step b is 2000V, and output rating is 300W.
According to the method for above-mentioned normal temperature deposition high interfacial strength diamond like carbon film material, the source takes place in the DC direct current plasma of opening described in the step c in the depositing device, and the output voltage that the source takes place described DC direct current plasma is 1000V, and electric current is 0.01A;
Hydrocarbon gas described in the steps d is acetylene C
2H
2, methane or benzene;
The rf frequency of the plasma generating source of alternation described in the step e is 13.56MHz, and radio-frequency voltage is 2000V, and output rating is 300W.
In the whole technology of above-mentioned normal temperature deposition high interfacial strength diamond like carbon film material, its base material is not heated, but remains on normal temperature state deposit.
The present invention has invented a kind of method that can solve the diamond like carbon film boundary strength by the detailed analysis to the boundary strength influence factor.The principal element that influences boundary strength has two aspects: the 1) adhesion strength of thin-film material and base material.This is that character by pairing material is determined, such as the interfacial diffusion of the formation of interfacial chemistry key, atom, interface crystal epitaxy etc.; 2) because the caused unrelieved stress of difference of material coefficient of thermal expansion coefficient.Common DLC diamond like carbon film material coefficient of thermal expansion coefficient (2.7 * 10
-6/ (500K)) compare much smallerly with metal base, DLC diamond like carbon film material internal will produce bigger compressive residual stress.In the former research, known at normal temperatures, the bonding strength of DLC diamond like carbon film material and metallic substance is very poor, even it is non-cohesive fully, but the present invention can solve the adhesion strength problem of diamond like carbon film and metal base preferably after adding a-Si:H:C transition intermediate layer of material; The main reason of finding to influence DLC diamond like carbon film boundary strength in the present invention research is the high compression unrelieved stress.The present invention is based on the normal temperature deposit, when reducing compressive residual stress, adds the a-Si:H:C transition material that better adhesion strength is arranged with metal base; But in the depositing of thin film process, because deposition and atomic and γ
-Thermionic bombardment still can produce local surfaces high temperature, particularly for the continuous DLC film of big area, still can produce bigger compressive residual stress.Thereby one of solution that the present invention adopts is that divided thin film is slit into small unit, and elementary boundary can discharge the unrelieved stress in the film, and the stress under compression that the contraction of base material produces each small cellar area is very little.When gordian technique of the present invention is to deposit the a-Si:H:C intermediate layer, the high-energy that utilizes point discharge to produce, make the a-Si:H:C intermediate layer produce non-sedimentary province at regional area, form discrete intermediate layer, and then produce discrete DLC diamond like carbon film layer, can discharge compressive residual stress effectively, thereby improve the bonding strength at interface.
Positive beneficial effect of the present invention:
1, utilize technical solution of the present invention, the compound DLC diamond like carbon film of the porous surface material structure of normal temperature deposition high interfacial bonding strength, solved the difficult problem of compressive residual stress in the film well, special construction by the composite anode in the normal temperature depositing device of the present invention system, under the condition of DC direct current plasma generation source discharge, form discontinuous porous a-Si:H:C transition thin film layer at substrate surface, further form porous surface DLC diamond like carbon film on this basis, can discharge effectively thus owing to the inconsistent caused compressive residual stress of thermal expansivity, thereby improve boundary strength.
2, in the deposition process of high interfacial strength diamond like carbon film of the present invention, realized the target of normal temperature deposit high interfacial strength DLC diamond like carbon film material; Normal temperature deposition can keep the accurate to dimension and the form accuracy of origianl component, for the production of Precision Machinery Elements provides condition; The normal temperature deposition can be widened the use restriction of base material simultaneously, can be used in the DLC diamond like carbon film deposition on low temperature-resistant material surface, has also widened the Application Areas of DLC diamond like carbon film material.
3, in the composite anode of normal temperature depositing device of the present invention, by go up the acute triangle notch of processing at refractory metal wire coil anode (for example tungsten filament coil anode), the point discharge effect takes place with this, the purpose of point discharge effect is in order to form vesicular structure on DLC diamond like carbon film surface, and the adjustable distance structure of composite anode, can adjust the pore density on DLC diamond like carbon film surface effectively, make under different situations, form appropriate porosity, and reach the releasing effect of the unrelieved stress of the best.
The array mode of source and alternation plasma generating source (source taking place as the RF radio frequency plasma) takes place in the DC direct current plasma that 4, is adopted in the normal temperature depositing device of the present invention, can either form the microvoid structure of certain density in metallic substrate surface, simultaneously also help forming the DLC diamond like carbon film layer of compact structure, thereby improve the wear resisting property of film greatly.When forming vesicular structure, use the DC direct current plasma that the source takes place, produce stable point discharge effect; In order to adjust DLC diamond like carbon film structure and to form fine and close thin film layer, adopt alternation plasma generating source (source taking place) as the RF radio frequency plasma, and refractory metal wire coil anode (as the tungsten filament coil electrode) is converted to hot filament, form heated filament assisted CVD chemical vapor deposition processes, improve depositing of thin film speed.
5, the present invention is in the normal temperature deposition method of DLC diamond like carbon film, with Si(CH
3)
4Be unstripped gas, both adhesion strength was preferably arranged in the deposition process with the DLC diamond like carbon film, with metal base the a-Si:H:C thin film layer of adhesion strength is preferably arranged again, thereby solved the problem that DLC diamond like carbon film material does not adhere to metal base at normal temperatures; The point discharge that utilizes the DC direct current plasma that the source takes place simultaneously and produce forms the porous surface structure, for the compound DLC diamond like carbon film that forms the discontinuous surface of porous is laid a good foundation, alleviate compressive residual stress in the film effectively, improved the bonding strength at interface thus.
6, the present invention is in the normal temperature deposition method of DLC diamond like carbon film, at first utilize the DC direct current plasma that the source takes place, refractory metal wire coil anode (as the tungsten filament coil anode) as main anode, the plane plate electrode is as secondary anode, at the a-Si:H:C film surface, form the transition DLC diamond like carbon film bottom of thinner thickness, its objective is: the vesicular structure that 1) forms DLC diamond like carbon film surface continuously, 2) for forming the DLC diamond like carbon film, (as the RF radio frequency method) in the alternating electric field of next step alternation plasma generating source lay the first stone, to form the DLC diamond like carbon film of same structure composition.In addition, utilize traditional RF radio frequency plasma deposition method can obtain the characteristics of the DLC diamond like carbon film structure of compact structure, on the basis that porous surface DLC diamond like carbon film bottom forms, can invade by atomic diffusion and atom effectively established transition DLC diamond like carbon film bottom is carried out structural adjustment, and continue to form the porous surface DLC diamond like carbon film of compact structure on this basis, increase the wear resistance of film.
7, the normal temperature deposition method of the discontinuous surperficial diamond like carbon film material of high interfacial bonding strength porous of the present invention is that condition has been created in the industrialization of DLC diamond like carbon film material, because the boundary strength problem can not practical application provide a kind of solution, this method has all obtained good effect on substrate surfaces such as Ti and Ti-6Al-4V, S45C, SUJ2, SKH51 tool steel for for a long time.
Show by technical scheme of the present invention: the spacing of anode and cathode is at 40～50mm, initial contact stress (hertz stress) is when 500MPa is following, the circulation destruction life-span of 1 μ m thickness thin film can reach 1,000,000 circulations above (Ball-on-Disk evaluation assessment), and keep frictional coefficient about 0.1, satisfy actual application level (referring to accompanying drawing 8 and Fig. 9).
8, the microstructure of product high interfacial bonding strength porous surface diamond like carbon film material of the present invention is referring to accompanying drawing 4～7, and its correlated performance is referring to accompanying drawing 8 and 9.
Four, description of drawings:
The normal temperature depositing device structural representation of Fig. 1 high interfacial strength diamond like carbon film of the present invention material;
Fig. 2 tungsten filament coil anode 4-2 structure diagram;
Fig. 3 is the I portion structure for amplifying synoptic diagram of Fig. 2;
During Fig. 4 cathode and anode spacing S=30mm, the microstructure of gained product high interfacial bonding strength of the present invention porous surface DLC diamond like carbon film;
During Fig. 5 cathode and anode spacing S=40mm, the microstructure of gained product high interfacial bonding strength of the present invention porous surface DLC diamond like carbon film;
During Fig. 6 cathode and anode spacing S=50mm, the microstructure of gained product high interfacial bonding strength of the present invention porous surface DLC diamond like carbon film;
During Fig. 7 cathode and anode spacing S=60mm, the microstructure of gained product high interfacial bonding strength of the present invention porous surface DLC diamond like carbon film;
Relation (S=50mm) between loading, rubbing characteristics and the abrasion cycle index of Fig. 8 product high interfacial bonding strength of the present invention porous surface DLC diamond like carbon film;
The loading of Fig. 9 product high interfacial bonding strength of the present invention porous surface DLC diamond like carbon film and circulation destroy the relation (S=50mm) between the life-span.
Number in the figure 1 is the bellows-type riser, 2 is grounding switch, 3 is the sediment chamber, and 4 is composite anode, and 4-1 is the dull and stereotyped anode (dull and stereotyped anode) in plane, 4-2 is the tungsten filament coil anode, 5 is base material, and 6 is the negative electrode Stage microscope, and 7 for cutting off switch, 8 are DC direct current plasma generation source, 9 for the source takes place in the RF radio frequency plasma, and 10 is RF radio frequency source impedance matching box, and 11 is direct supply, 12 is insulation covering, 13 is the unstripped gas origin system, and 14 is lead, and 15 is vacuum extractor, 16 is insulation covering (vitrified pipe), and 17 is triangle tapered point groove.
Five, embodiment:
Following examples only in order to further specify the present invention, do not limit content of the present invention.
Embodiment one:
A kind of normal temperature depositing device of high interfacial bonding strength porous surface diamond like carbon film material:
Referring to Fig. 1, Fig. 2, Fig. 3, normal temperature depositing device of the present invention contains sediment chamber 3, is communicated with unstripped gas intake ducting 13 and vacuum extractor 15 with sediment chamber 3.3 inner bottom parts are provided with negative electrode Stage microscope 6 in the sediment chamber, and base material 5 is positioned on the negative electrode Stage microscope 6, and negative electrode Stage microscope 6 is connected with the negative pole of plasma generating source.In the present embodiment, plasma generating source comprises two portions, and a part is that source 8 takes place the DC direct current plasma, and another part is an alternation plasma generating source 9, for example adopts the RF radio frequency plasma that the source takes place.The positive pole of two plasma generating sources is connected with sediment chamber's 3 shells, and the negative electrode that the source takes place two ions is connected with negative electrode 6 by isolator 7 respectively.The source can also take place or for high frequency plasma the source takes place or is microwave plasma generation source for the DC pulse plasma in described alternation plasma generating source, and other alternation plasma generating sources.
3 upper inside are provided with composite anode 4 in the sediment chamber, this composite anode 4 comprises the tungsten filament coil anode 4-2 of a dull and stereotyped anode 4-1 and a most advanced and sophisticated groove 17 of band triangle acute angle, so that formation highfield, its middle plateform anode 4-1 is positioned at tungsten filament coil anode 4-2 upside, and dull and stereotyped anode 4-1 all is connected with the plasma generating source anode with tungsten filament coil anode 4-2.In fact, composite anode 4 is electrically connected with sediment chamber's 3 shells, and sediment chamber's 3 shells are connected with ground wire.Upside in sediment chamber 3 also is equipped with a riser 1 that is used to adjust distance between composite anode 4 and the negative electrode 6, this riser adopts bellows-type riser 1, thereby makes composite anode 4 move up and down the distance of adjusting between composite anode 4 and the negative electrode 6 by adjusting riser 1; Insulate by vitrified pipe 16 between described dull and stereotyped anode 4-1 and the refractory metal wire coil anode 4-2, directly conducting.
When alternating electric field deposition DLC thin-film material, described tungsten filament coil anode 4-2 provides the thermal ionization field as hot filament, and does not have substrate 5 heating systems for 6 times at the negative electrode Stage microscope.As seen tungsten filament coil anode 4-2 plays two effects in this equipment, and the one, be used for heating, utilize the high temperature (1800-2400 ℃) on hot tungsten filament surface, produce highdensity plasma body, increase depositing of thin film speed.Be the highfield that utilizes triangle acute angle tip on the tungsten filament coil electrode in addition, form the high-density current of local point discharge, form the hole of certain density on bottom DLC diamond like carbon film surface, hole density and diameter can be adjusted by adjusting interelectrode distance and power supply power input.Concrete structure is that the two ends of tungsten filament coil anode 4-2 are connected with the two ends of a direct supply that is used to heat 11 respectively, are fixed together by insulation covering 12 between the two ends lead 14 of tungsten filament coil anode 4-2 and the sediment chamber 3.And the supply lead of this tungsten filament coil anode 4-2 is equipped with on the output terminal of the described direct supply that is used to heat 11 and cuts off switch 7 by a grounding switch 2 and sediment chamber's shell 3 break-makes.This grounding switch 2 is used for selecting tungsten filament coil anode 4-2 is communicated with direct supply 11 two ends, perhaps is communicated with the positive pole (being sediment chamber's shell) of plasma generating source.
About composite anode 4, the change aspect electrode geometry stands good, for example combined electrode of being constituted of cylindrical anode and cylindrical tungsten filament coil electrode etc.
A kind of method of utilizing above-mentioned normal temperature depositing device normal temperature deposition high interfacial strength diamond like carbon film material, the detailed step of described method is as follows:
A, at first adjust that the distance between the composite anode 4 and negative electrode 6 is 30mm in the above-mentioned depositing device, the placement surface roughness is S45C(or other metal bases of Φ 50 diameters of Ra0.05 on negative electrode Stage microscope 6 then) circular base material 5, utilize the vacuum extractor 15 that is communicated with sediment chamber 3 that the vacuum pressure in the sediment chamber 3 is evacuated to 5 * 10
-3Pa;
B, then source 8 being taken place the DC direct current plasma in the depositing device closes, and by cutting off switch 7 and equipment disconnection, open the Ar source of the gas air intake valve 13 that is communicated with sediment chamber 3, feed Ar gas, vacuum pressure in the adjustment sediment chamber 3 is to 10Pa, sediment chamber's 3 internal pressures reach that the flow of Ar gas remains unchanged behind the 10Pa, opening the direct supply 11 that is used to heat in the heat filament device and RF radio frequency plasma, the rf bias that source 9 takes place source 9(RF radio frequency plasma takes place is 2000V, output rating is 300W), adopt conventional heated filament assisted CVD method that base material 5 is carried out 10 minutes plasma bombardment, remove the pollutent on base material 5 surfaces;
The deposition process of c, a-Si:H:C intermediate layer: close the direct supply 11 and the RF radio frequency plasma that are used to heat in Ar source of the gas air intake valve 13, the heat filament device then source 9 takes place, disconnect with equipment by cutting off switch 7 respectively, make tungsten filament coil anode 4-2 be in ground state, open tetramrthylsilane (CH then
3)
4Gas source air intake valve 13 feeds tetramrthylsilane (CH
3)
4Gas is adjusted vacuum pressure in the sediment chamber 3 to 15Pa, and sediment chamber's 3 internal pressures reach Si (CH behind the 15Pa
3)
4The flow of gas remains unchanged, the output voltage of opening the 8(DC direct current plasma generation source 8, DC direct current plasma generation source in the depositing device is 1000V, electric current is 0.01A), between tungsten filament coil anode 4-2 and base material 5 plasma discharge takes place, deposition a-Si:H:C middle transition layer film 20 minutes;
The deposition process of d, DLC diamond like carbon film material: after the thin film deposition of a-Si:H:C intermediate layer, reduce Si (CH gradually
3)
4The flow of gas is opened C simultaneously
2H
2Gas and H
2The air intake valve 13 of gas imports C
2H
2Gas and H
2Gas, C
2H
2Gas and H
2The flow proportional of gas between the two is 1:4, Si (CH after 10～15 minutes
3)
4The flow of gas is gradually reduced to zero, and this moment, the air intake valve of tetramethylsilane gas source was closed fully, by the air inlet needle-valve with C
2H
2The flow of gas is adjusted to 5sccm, H
2The flow of gas is adjusted to 20sccm, and the vacuum pressure in the sediment chamber 3 remains on 25Pa, deposition DLC diamond like carbon film bottom 15 minutes; Then source 8 is taken place in the DC direct current plasma and close, disconnect with equipment by cutting off switch 7;
E, transfer switch 2 is placed non-ground state, open the direct supply 11 that is used to heat in the heat filament device then, feed electric current to tungsten filament coil anode 4-2, the rf frequency of opening 9(RF radio frequency plasma generation source 9, RF radio frequency plasma generation source is 13.56MHz, radio-frequency voltage is 2000V, output rating is 300W), enter the C in the sediment chamber 3 this moment
2H
2Gas flow still keeps 5sccm, H
2Gas flow keeps 20sccm, vacuum pressure in the sediment chamber is 25Pa, deposition DLC diamond like carbon film layer 45 minutes, obtain the diamond like carbon film of composite structure after the deposition, source 9 and the direct supply 11 that is used for heat filament take place in orderly close-down RF radio frequency plasma then, disconnect with equipment by cutting off switch 7 respectively, and close C
2H
2Gas source and H
2The air intake valve of gas source obtains the discontinuous surperficial diamond like carbon film material of porous (microstructure of products obtained therefrom sees accompanying drawing 4 for details) of product high interfacial bonding strength of the present invention at last.
The thickness of the discontinuous surperficial diamond like carbon film material of the porous of products obtained therefrom high interfacial bonding strength is 1 μ m, and the aperture is that whole deposition process is carried out at normal temperatures about 5-8 μ m.
Embodiment two: basic identical with embodiment one, difference is:
The normal temperature depositing device of the discontinuous surperficial diamond like carbon film material of a kind of high interfacial bonding strength porous is identical with embodiment one.
A kind of method of utilizing above-mentioned normal temperature depositing device normal temperature deposition high interfacial strength diamond like carbon film material is with embodiment one difference:
Among the step a: adjust that the distance between the composite anode 4 and negative electrode 6 is 40mm in the above-mentioned depositing device.
The thickness of the discontinuous surperficial diamond like carbon film material of the porous of products obtained therefrom high interfacial bonding strength is 1 μ m, from the microstructure photograph shown in the accompanying drawing 5 as can be known, formed middle density porous structure on DLC diamond like carbon film surface, this structure makes the DLC diamond like carbon film show as discontinuity, and basic not variation is compared in the aperture with embodiment one.
Embodiment three: basic identical with embodiment one, difference is:
The normal temperature depositing device of the discontinuous surperficial diamond like carbon film material of a kind of high interfacial bonding strength porous is identical with embodiment one.
A kind of method of utilizing above-mentioned normal temperature depositing device normal temperature deposition high interfacial strength diamond like carbon film material is with embodiment one difference:
Among the step a: adjust that the distance between the composite anode 4 and negative electrode 6 is 50mm in the above-mentioned depositing device.
The thickness of the discontinuous surperficial diamond like carbon film material of the porous of products obtained therefrom high interfacial bonding strength is 1 μ m, from the microstructure photograph shown in the accompanying drawing 6 as can be known, formed middle density porous surface structure on DLC diamond like carbon film surface, its continuity is compared with embodiment two to some extent to be increased, and the aperture also slightly reduces.
Above-mentioned sedimentary high interfacial strength diamond like carbon film is carried out the rubbing characteristics evaluation with the Ball-on-Disk method.Accompanying drawing 8 is the relations between loading, frictional coefficient and the abrasion cycle index.Can see that the increase of loading has very big influence to the abrasion life-span, but to almost not influence of frictional coefficient, frictional coefficient is about 0.1.Accompanying drawing 9 is loading and relations between the circulation destruction life-span of present embodiment gained high interfacial strength diamond like carbon film, along with destroying the life-span, the increase of loading circulation reduces rapidly, but when contact stress is that 544MPa is when following, its destruction life-span has surpassed more than 1,000,000 circulations, can be used for practical application.
Embodiment four: basic identical with embodiment one, difference is:
A kind of normal temperature depositing device of high interfacial bonding strength porous surface diamond like carbon film material is identical with embodiment one.
A kind of method of utilizing above-mentioned normal temperature depositing device normal temperature deposition high interfacial strength diamond like carbon film material is with embodiment one difference:
Among the step a: adjust that the distance between the composite anode 4 and negative electrode 6 is 60mm in the above-mentioned depositing device.
The thickness of the discontinuous surperficial diamond like carbon film material of the porous of products obtained therefrom high interfacial bonding strength is 1 μ m, from the microstructure photograph shown in the accompanying drawing 7 as can be known, formed low density porous surface structure on DLC diamond like carbon film surface, almost become the continuity film, the aperture does not have to change substantially.
Claims (10)
1. the normal temperature depositing device of a high interfacial strength diamond like carbon film material, contain the sediment chamber, be communicated with unstripped gas intake ducting and vacuum extractor with the sediment chamber, be provided with the negative electrode Stage microscope that is connected with the plasma generating source negative pole at sediment chamber's inner bottom part, be provided with and the anodal anode that is connected of plasma generating source at the deposition chamber interior upside, wherein anode is electrically connected with the sediment chamber, the sediment chamber is connected with ground wire, and heat filament device, it is characterized in that: described anode is a composite anode, this composite anode comprises a dull and stereotyped anode and a refractory metal wire coil anode, its middle plateform anode is positioned at refractory metal wire coil anode upside, and dull and stereotyped anode all is connected with the plasma generating source anode with refractory metal wire coil anode; Described plasma generating source is that source and an alternation plasma generating source take place a DC direct current plasma, and the anode of two plasma generating sources is connected with sediment chamber's shell, and the negative electrode of two plasma generating sources is connected with negative electrode by cutting off switch respectively.
2. normal temperature depositing device according to claim 1 is characterized in that: on described refractory metal silk surface, certain distance offers the triangular notch of band acute angle at interval, and the point of this acute angle is not less than the par, constitutes the point discharge point.
3. normal temperature depositing device according to claim 1 and 2 is characterized in that: described refractory metal wire coil anode is the tungsten filament coil anode, perhaps is molybdenum filament coil anode, perhaps is tantalum wire coil anode.
4. normal temperature depositing device according to claim 1, it is characterized in that: described heat filament device comprises refractory metal wire coil, the direct supply that is used to heat and ground connection switch on and off, the two ends of this refractory metal wire coil are connected with the positive and negative electrode of the direct supply that is used to heat respectively, and the supply lead of this refractory metal wire coil is communicated with sediment chamber's shell by a grounding switch, and the partition switch is installed on the output terminal of the direct supply that is used to heat simultaneously.
5. normal temperature depositing device according to claim 1 is characterized in that: described alternation plasma generating source is that the source takes place the RF radio frequency plasma, perhaps for the DC pulse plasma source takes place or for high frequency plasma generation source or be microwave plasma generation source.
6. normal temperature depositing device according to claim 1 is characterized in that: insulated by vitrified pipe between described dull and stereotyped anode and the refractory metal wire coil anode, directly conducting; Upside in the sediment chamber also is equipped with a riser that is used to adjust distance between composite anode and the negative electrode, thereby makes composite anode move up and down the distance of adjusting between composite anode and the negative electrode by adjusting riser.
7. a method of utilizing the described normal temperature depositing device of claim 1 normal temperature deposition high interfacial strength diamond like carbon film material is characterized in that, said method comprising the steps of:
A, at first adjust described in the claim 1 distance between the composite anode and negative electrode in the depositing device, on the negative electrode Stage microscope, place base material then, utilize the vacuum extractor that is communicated with the sediment chamber that the vacuum pressure in the sediment chamber is evacuated to and be not less than 5 * 10
-3Pa;
B, then the DC direct current plasma generation source in the depositing device is closed, and by cutting off the disconnection of switch and equipment, open the Ar source of the gas air intake valve that is communicated with the sediment chamber, feed Ar gas, adjust vacuum pressure to the 10～12Pa in the sediment chamber, sediment chamber's internal pressure reaches that the flow of Ar gas remains unchanged behind 10～12Pa, open the direct supply and the alternation plasma generating source that are used to heat in the heat filament device, adopt conventional heated filament assisted CVD method that base material is carried out 8～15 minutes plasma bombardment, remove the pollutent of substrate surface;
The deposition process of c, a-Si:H:C intermediate layer: close the direct supply and the alternation plasma generating source that are used to heat in Ar source of the gas air intake valve, the heat filament device then, disconnect by cutting off switch and equipment respectively, open tetramrthylsilane (CH then
3)
4The gas source air intake valve feeds tetramrthylsilane (CH
3)
4Gas is adjusted vacuum pressure to the 15～17Pa in the sediment chamber, and sediment chamber's internal pressure reaches Si (CH behind 15～17Pa
3)
4The flow of gas remains unchanged, and the source takes place the DC direct current plasma of opening in the depositing device, between refractory metal wire coil anode and base material plasma discharge takes place, deposition a-Si:H:C middle transition layer film 18～22 minutes;
The deposition process of d, DLC diamond like carbon film material: after the thin film deposition of a-Si:H:C intermediate layer, reduce Si (CH gradually
3)
4The flow of gas is opened hydrocarbon gas and H simultaneously
2The air intake valve of gas imports hydrocarbon gas and H
2Gas, hydrocarbon gas and H
2The flow proportional of gas between the two is 1:4, Si (CH after 10～15 minutes
3)
4The flow of gas is reduced to zero, and this moment, the air intake valve of tetramethylsilane gas source was closed fully, by the air inlet needle-valve flow of hydrocarbon gas is adjusted to 5sccm, H
2The flow of gas is adjusted to 20sccm, and the vacuum pressure in the sediment chamber remains on 25Pa, deposition DLC diamond like carbon film bottom 15～18 minutes; Then DC direct current plasma generation source is closed, disconnected by cutting off switch and equipment;
E, open the direct supply that is used to heat in the heat filament device then, feed electric current to refractory metal wire coil anode, open the alternation plasma generating source, the hydrocarbon gas flow in this moment sediment chamber still keeps 5sccm, H
2Gas flow keeps 20sccm, vacuum pressure in the sediment chamber is 25Pa, deposition DLC thin film layer 42～45 minutes, obtain the diamond like carbon film of composite structure after the deposition, the direct supply of then closing the alternation plasma generating source in order and being used to heat, disconnect by cutting off switch and equipment respectively, and close hydrocarbon gas source and H
2The air intake valve of gas source obtains the discontinuous surperficial diamond like carbon film material of porous of product high interfacial bonding strength of the present invention at last.
8. the method for normal temperature deposition high interfacial strength diamond like carbon film material according to claim 7, it is characterized in that: the distance between composite anode described in the step a and the negative electrode is 30～60mm.
9. the method for normal temperature deposition high interfacial strength diamond like carbon film material according to claim 7, it is characterized in that: the rf bias of the plasma generating source of alternation described in the step b is 2000V, output rating is 300W.
10. the method for normal temperature deposition high interfacial strength diamond like carbon film material according to claim 7, it is characterized in that: the source takes place in the DC direct current plasma of opening described in the step c in the depositing device, the output voltage that the source takes place described DC direct current plasma is 1000V, and electric current is 0.01A;
Hydrocarbon gas described in the steps d is acetylene C
2H
2, methane or benzene;
The rf frequency of the plasma generating source of alternation described in the step e is 13.56MHz, and radio-frequency voltage is 2000V, and output rating is 300W.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260859A (en) * | 2010-05-31 | 2011-11-30 | 株式会社捷太格特 | Method of producing coated member |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02232371A (en) * | 1989-03-03 | 1990-09-14 | Nec Corp | Thin-film forming device |
| JP2004027244A (en) * | 2002-06-21 | 2004-01-29 | Canon Inc | Film deposition system, film deposition method, electron emitter using the method, electron source and production method for image forming apparatus |
| CN2666928Y (en) * | 2003-09-23 | 2004-12-29 | 青岛科技大学 | Apparatus for chemical gas phase depositing diamond film by plasma heat wire method |
| CN1831187A (en) * | 2006-03-27 | 2006-09-13 | 南京航空航天大学 | Heater array electrode system used for stable growth of diamond membrane with large area |
| CN101591775A (en) * | 2009-06-18 | 2009-12-02 | 天津理工大学 | Be applicable to the thin film deposition system device of diamond heat-sink membrane |
| CN201962349U (en) * | 2010-12-22 | 2011-09-07 | 郑锦华 | Normal temperature deposition equipment for high boundary strength diamond film material |
-
2010
- 2010-12-22 CN CN 201010599609 patent/CN102011102B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02232371A (en) * | 1989-03-03 | 1990-09-14 | Nec Corp | Thin-film forming device |
| JP2004027244A (en) * | 2002-06-21 | 2004-01-29 | Canon Inc | Film deposition system, film deposition method, electron emitter using the method, electron source and production method for image forming apparatus |
| CN2666928Y (en) * | 2003-09-23 | 2004-12-29 | 青岛科技大学 | Apparatus for chemical gas phase depositing diamond film by plasma heat wire method |
| CN1831187A (en) * | 2006-03-27 | 2006-09-13 | 南京航空航天大学 | Heater array electrode system used for stable growth of diamond membrane with large area |
| CN101591775A (en) * | 2009-06-18 | 2009-12-02 | 天津理工大学 | Be applicable to the thin film deposition system device of diamond heat-sink membrane |
| CN201962349U (en) * | 2010-12-22 | 2011-09-07 | 郑锦华 | Normal temperature deposition equipment for high boundary strength diamond film material |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260859A (en) * | 2010-05-31 | 2011-11-30 | 株式会社捷太格特 | Method of producing coated member |
| CN102260859B (en) * | 2010-05-31 | 2014-04-23 | 株式会社捷太格特 | Method of producing coated member |
| CN103572249A (en) * | 2012-08-07 | 2014-02-12 | 株式会社电装 | Method and device for forming amorphous carbon coating |
| CN109518160B (en) * | 2018-12-26 | 2021-10-01 | 深圳市爱能森科技有限公司 | Surface treatment process |
| CN109518160A (en) * | 2018-12-26 | 2019-03-26 | 深圳市爱能森科技有限公司 | A kind of process of surface treatment |
| CN109825808A (en) * | 2019-03-01 | 2019-05-31 | 许世鹏 | A kind of doped diamond film preparation device and method |
| CN109825808B (en) * | 2019-03-01 | 2024-05-24 | 酒泉职业技术学院(甘肃广播电视大学酒泉市分校) | Doped diamond-like film preparation device and method |
| CN110512195A (en) * | 2019-09-20 | 2019-11-29 | 武汉工程大学 | A kind of tubular material inner surface carries out the method and device of MPCVD |
| CN110670077A (en) * | 2019-10-29 | 2020-01-10 | 苏州创瑞机电科技有限公司 | Corrosion-resistant surface treatment method for coil shell and corrosion-resistant coil shell |
| CN110670077B (en) * | 2019-10-29 | 2022-01-25 | 苏州创瑞机电科技有限公司 | Corrosion-resistant surface treatment method for coil shell and corrosion-resistant coil shell |
| CN112951707A (en) * | 2019-12-11 | 2021-06-11 | 株洲中车时代电气股份有限公司 | Film and preparation method and application thereof |
| CN113265642A (en) * | 2021-05-13 | 2021-08-17 | 郑州大学 | Method for depositing diamond-like carbon film on inner wall surface of metal cylinder (or tube) with large length-diameter ratio |
| CN113802112A (en) * | 2021-08-19 | 2021-12-17 | 郑州大学 | Deposition method of high-interface-strength DLC film with bonding layer and transition layer |
| CN113802112B (en) * | 2021-08-19 | 2023-10-31 | 郑州大学 | Deposition method of high interface strength DLC film with bonding layer and transition layer |
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