The normal temperature depositing device and the method thereof of high interfacial strength DLC film material
Technical field
The present invention relates to a kind of deposition method and equipment of DLC DLC film material, particularly relate to the normal temperature depositing device and the normal temperature deposition method thereof of the discontinuous surperficial DLC film material of a kind of high interfacial bonding strength porous.
Background technology
DLC film (Diamond-like Carbon Films is called for short the DLC film) is that one type of characteristic such as hardness, optics, electricity, chemistry and tribology all is similar to adamantine amorphous carbon-film.For example, it has characteristics such as high firmness, 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 DLC 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 DLC 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 DLC film to a certain extent.
Quasi-diamond (DLC) thin-film material is most representative one type of 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 technological emphasis of various countries' research.Developed multiple middle transition dielectric material technology at present, be configured with: Si+DLC, soaked carbon+Cr+DLC, Cr/W+DLC and atom and inject nitriding treatment+DLC etc. as handling the DLC DLC film for the compound surface of mechanical component.Along with continuous technological development and research, its method of manufacture also constantly increases, for example: the improvement of PVD physical vaporous deposition technology, can produce no hydrogen DLC DLC film, and be successfully used to the manufacturing of motor car engine piston-ring and connecting bar and crankshaft.Domestic present DLC DLC 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. like 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 DLC film made technical elements 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 through being coated with boron.Boride, silicon, metallic carbide, metal nitride etc. can both solve the interface problem of DLC DLC film as intermediate layer in fact; But apply and expensive and producing apparatus complicated that sedimentary two procedures will cause the DLC DLC 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 DLC film material prepn 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 DLC film of low temperature depositing changeable refractive index ", and this patent of invention adopts existing Vakuumkammer and Process configuration; At room temperature, regulate substrate to the distance that has between the grid Kaufman ion source; The vacuum tightness of regulating Vakuumkammer 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 Vakuumkammer 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 the DLC 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, and methane amide is an electrolytic solution, under normal temperature condition; Through between negative and positive two electrodes, applying the volts DS of 3~30V, can on the indium tin oxide-coated glass negative electrode, deposit DLC 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 the Ti content in the TiC layer through 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 DLC film high firmness 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 that the present invention will solve is: normal temperature depositing device and normal temperature deposition method thereof that the discontinuous surperficial DLC film material of a kind of high interfacial bonding strength porous is provided.The crucial difficult problem that can solve the existence of DLC DLC film made technical elements through technical scheme of the present invention is the boundary strength problem.Utilize technical scheme of the present invention to prepare DLC DLC film material, can solve the film inner high voltage residual stress problems that contracts well, thereby prepare the discontinuous surperficial DLC film material of the porous with high interfacial bonding strength.
In order to address the above problem, the technical scheme that the present invention adopts is:
The present invention provides a kind of normal temperature depositing device of high interfacial strength DLC film material; Contain the sediment chamber, be communicated with virgin gas intake ducting and vacuum extractor with the sediment chamber, inner bottom part is provided with the negative electrode Stage microscope that is connected with the plasma generating source negative pole in the sediment chamber; 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, and the sediment chamber is connected with ground wire, and the heat filament device; Said anode is a composite anode; This composite anode comprises a dull and stereotyped anode and a refractory metal wire coil anode, and 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; Said 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 through cutting off switch respectively.The fusing point of refractory metal wire coil described herein is not less than 1800 ℃.
On said 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.
Said 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.
Said 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 through 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.
The source takes place for the RF radio frequency plasma in said alternation plasma generating source, perhaps the source takes place, perhaps the source takes place, perhaps for microwave plasma source, perhaps other alternation plasma generating sources take place for high frequency plasma for the DC pulse plasma.
Insulate by vitrified pipe between said 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 between adjustment composite anode and the negative electrode through the adjustment 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 DP, 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 DLC 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 settling chamber; Feed Ar gas; Vacuum pressure to 10~12Pa in the adjustment settling chamber; Settling chamber's internal pressure reaches that the flow of Ar gas remains unchanged behind 10~12Pa; Open the dc source 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 pollutant 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, break off through cutting off switch and equipment respectively, open tetramrthylsilane (CH then
3)
4The gas source air intake valve feeds tetramrthylsilane (CH
3)
4Gas, vacuum pressure to the 15~17Pa of adjustment in the sediment chamber, 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 DLC 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 TMS gas source was closed fully, through 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 DLC film bottom 15~18 minutes; Then DC direct current plasma generation source is closed, broken off through 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; Deposit DLC thin film layer 42~45 minutes, obtain the DLC film of composite structure after the deposition, then orderly close-down alternation plasma generating source and the direct supply that is used to heat; Break off through cutting off switch and equipment respectively, and close hydrocarbon gas source and H
2The air intake valve of gas source obtains the discontinuous surperficial DLC 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 DLC 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 DLC 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 DLC 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 said 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 DLC 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 DLC film boundary strength through 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 determines, such as the interfacial diffusion of the formation of interface chemistry key, atom, interface crystal epitaxy etc.; 2) because the caused unrelieved stress of difference of material coefficient of thermal expansion coefficient.Common DLC DLC film material coefficient of thermal expansion coefficient (2.7 * 10
-6/ (500K)) compare much smallerly with metal base, DLC DLC film material internal will produce bigger compressive residual stress.In the former research; Known at normal temperatures; The bonding strength of DLC DLC film material and metallic substance is very poor; Even non-cohesive fully, but the present invention can solve the adhesion strength problem of DLC film and metal base preferably after adding a-Si:H:C transition intermediate layer of material; The main reason of in the present invention research, finding to influence DLC DLC film boundary strength 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, form discrete intermediate layer, and then produce discrete DLC DLC film layer at regional area; Can discharge compressive residual stress effectively, thereby improve the bonding strength at interface.
Positive beneficial effect of the present invention:
1, utilizes technical scheme of the present invention; The compound DLC DLC 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, through the special construction of 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 DLC film on this basis, can discharge effectively thus, thereby improve boundary strength owing to the inconsistent caused compressive residual stress of thermal expansivity.
2, in the deposition process of high interfacial strength DLC film of the present invention, realized the target of normal temperature deposit high interfacial strength DLC DLC 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 DLC film deposition on low temperature-resistant material surface, has also widened the Application Areas of DLC DLC film material.
3, in the composite anode of normal temperature depositing device of the present invention; Through go up the oxygon notch of processing at refractory metal wire coil anode (for example tungsten filament coil anode); With this point discharge effect takes place, the purpose of point discharge effect is in order to form vesicular structure on DLC DLC film surface, and the adjustable distance structure of composite anode; Can adjust the pore density on DLC DLC film surface effectively; Make under condition of different, 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 like 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 DLC 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 DLC film structure and to form fine and close thin film layer; Adopt alternation plasma generating source (source taking place) like the RF radio frequency plasma; And convert refractory metal wire coil anode (like the tungsten filament coil electrode) into 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 DLC film, with Si (CH
3)
4Be virgin gas; Both adhesion strength was preferably arranged in the deposition process with the DLC DLC 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 DLC 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 DLC 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 DLC film; At first utilize the DC direct current plasma that the source takes place; As main anode, the plane plate electrode is as secondary anode, at the a-Si:H:C film surface refractory metal wire coil anode (like the tungsten filament coil anode); Form the transition DLC DLC film bottom of thinner thickness; Its objective is: 1) form the vesicular structure on DLC DLC film surface continuously, 2) for forming the DLC DLC film, (like 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 DLC film of same structure composition.In addition; Utilize traditional RF radio frequency plasma deposition method can obtain the characteristics of the DLC DLC film structure of compact structure; On the basis that porous surface DLC DLC film bottom forms; Can invade through atomic diffusion and atom effectively established transition DLC DLC film bottom is carried out structural adjustment, and continue to form the porous surface DLC DLC film of compact structure on this basis, increase the wear resistance of film.
7, the normal temperature deposition method of the discontinuous surperficial DLC film material of high interfacial bonding strength porous of the present invention is that condition has been created in the industrialization of DLC DLC 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 TS for for a long time.
Show through 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 DLC 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 DLC 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 DLC 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 DLC 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 DLC 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 DLC 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 DLC film;
The loading of Fig. 9 product high interfacial bonding strength of the present invention porous surface DLC DLC film and circulation destroy the relation (S=50mm) between the life-span.
Label 1 is the bellows-type riser among the figure, and 2 is grounding switch, and 3 is the sediment chamber, and 4 is composite anode; 4-1 is the dull and stereotyped anode (dull and stereotyped anode) in plane, and 4-2 is the tungsten filament coil anode, and 5 is base material, and 6 is the negative electrode Stage microscope; 7 for cutting off switch, and 8 for the source takes place the DC direct current plasma, and 9 for the source takes place the RF radio frequency plasma, and 10 is RF radio frequency source impedance matching box; 11 is direct supply, and 12 is insulation covering, and 13 is the virgin gas origin system, and 14 is lead; 15 is vacuum extractor, and 16 is insulation covering (vitrified pipe), and 17 is triangle tapered point groove.
Five, embodiment:
Following examples have been merely and have further specified 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 DLC 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 virgin 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 through isolator 7 respectively.The source can also take place for the DC pulse plasma in said alternation plasma generating source, or for the source takes place, or is microwave plasma generation source in high frequency plasma, and other alternation plasma generating sources.
3 inner upper side 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 between adjustment composite anode 4 and the negative electrode 6 through adjustment riser 1; Insulate by vitrified pipe 16 between said 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, said 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.It is thus clear that tungsten filament coil anode 4-2 plays two effects in this equipment, 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 to utilize the most advanced and sophisticated highfield of triangle acute angle 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 DLC film surface, hole density and diameter can be adjusted through adjustment 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 through 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 said direct supply that is used to heat 11 and cuts off switch 7 through 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.
Vacuum extractor 15 adopts the two-stage vacuum system, and main vacuum pump adopts molecular pump or DP, and secondary pump adopts rotary-vane vaccum pump, guarantees that system limits vacuum tightness reaches 5 * 10
-3More than.
A kind of method of utilizing above-mentioned normal temperature depositing device normal temperature deposition high interfacial strength DLC film material, the detailed step of said method is following:
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 the circular base material 5 of S45C (or other metal bases) of Φ 50 diameters of Ra0.05 on negative electrode Stage microscope 6 then, utilizes 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 is taken place in the DC direct current plasma in the depositing device and close; And, open the Ar source of the gas air intake valve 13 that is communicated with sediment chamber 3 through cutting off switch 7 and equipment disconnection, 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, open the direct supply 11 that is used to heat in the heat filament device and with the RF radio frequency plasma source 9 (rf bias that source 9 takes place the RF radio frequency plasma is 2000V, and output rating is 300W) take place; 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; Break off with equipment through 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, the vacuum pressure in the adjustment sediment chamber 3 is to 15Pa, and sediment chamber's 3 internal pressures reach Si (CH behind the 15Pa
3)
4The flow of gas remains unchanged; Opening DC direct current plasma in the depositing device source 8 takes place (output voltage that source 8 takes place the DC direct current plasma 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 DLC 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 TMS gas source was closed fully, through 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 DLC film bottom 15 minutes; Then source 8 is taken place in the DC direct current plasma and close, break off with equipment through 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, (rf frequency that source 9 takes place the RF radio frequency plasma is 13.56MHz, and radio-frequency voltage is 2000V to open RF radio frequency plasma generation source 9; Output rating is 300W), get into 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; Deposit DLC DLC film layer 45 minutes, obtain the DLC 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; Break off with equipment through cutting off switch 7 respectively, and close C
2H
2Gas source and H
2The air intake valve of gas source obtains the discontinuous surperficial DLC 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 DLC 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 DLC 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 DLC 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 DLC film material of the porous of products obtained therefrom high interfacial bonding strength is 1 μ m; Can know from the microstructure photograph shown in the accompanying drawing 5; Formed middle density porous structure on DLC DLC film surface; This structure makes the DLC DLC 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 DLC 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 DLC 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 DLC film material of the porous of products obtained therefrom high interfacial bonding strength is 1 μ m; Can know from the microstructure photograph shown in the accompanying drawing 6; Formed middle density porous surface structure on DLC DLC 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 DLC 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 that the loading and the circulation of present embodiment gained high interfacial strength DLC film destroys the relation between the life-span; 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 DLC 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 DLC 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 DLC film material of the porous of products obtained therefrom high interfacial bonding strength is 1 μ m; Can know from the microstructure photograph shown in the accompanying drawing 7; Formed low density porous surface structure on DLC DLC film surface, almost become the continuity film, the aperture does not have to change basically.