CN100467664C - Method for manufacturing diamond-like film and part with coating manufactured thereby - Google Patents
Method for manufacturing diamond-like film and part with coating manufactured thereby Download PDFInfo
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- CN100467664C CN100467664C CNB2005100476790A CN200510047679A CN100467664C CN 100467664 C CN100467664 C CN 100467664C CN B2005100476790 A CNB2005100476790 A CN B2005100476790A CN 200510047679 A CN200510047679 A CN 200510047679A CN 100467664 C CN100467664 C CN 100467664C
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Abstract
The invention provides the radio-frequency excited plasma enhancement chemical vapour deposition method, comprising the following steps: depositing a layer of sheet metal on the background, then depositing nitride or carbonide on sheet metal, and depositing adamantine carbon film on the nitride or carbonide. The invention also provides the part with composite coating which is made by the method, and the base material of the part is metal or ceramic or glass or organic resin. The invention provides the radio-frequency excited plasma enhancement chemical vapour deposition method device, which comprises more than one metal sputtering source, and evacuated chamber which comprises plasma generating chamber and plasma treatment chamber. In the plasma treatment chamber there is plasma treatment chamber to make the coating homogeneous and isotropism. Adjust electric voltage, current and Ar, N2 and carbonaceous gas content to deposit high adhesive force adamantine carbon film.
Description
Technical field
The invention belongs to the material surface machining technology, particularly relate to the method for depositing diamond-like carbon film on base material and implement the device of this method and the parts of the band coating film made with this method.
Background technology
(the Diamond-like Carbon films of plating diamond-like carbon film on metal partss such as iron and steel, hereinafter to be referred as the DLC film) as wear resistant friction reducing coating and self-lubricating material, have reality and potential economic worth, it can be applied in such as fields such as drill bit, gear, bearing, mould, drift and medicine equipments, but at present because the applying of DLC membrane technique that had many effects limit.
At first, owing to the difference of performance and the existence of interfacial compressive stress between matrix and the film, common DLC film and most metal be the poor adhesive force between the steel substrate particularly, even is difficult to direct deposition, and this just exists film, basic suitability problem.
Chinese patent application case 01121264.0 discloses and a kind of metal oxide has been included in the amorphous hard carbon films to improve film-substrate cohesion and to reduce the processing method of frictional coefficient, contain oxide compound in its film and mainly be the oxide compound of silicon, titanium, boron and tungsten, wherein oxygen level reaches 0.1～10at%, the thickness of film reaches 5～10 μ m, and it is the suitability that solves film, base with oxide compound.
Chinese patent application case 03145846.7 discloses a kind of carbon film parts and method for making thereof covered, and it is to form mixolimnion on substrate at least a portion, and this mixolimnion comprises element and the tungsten that constitutes substrate, forms tungsten film on this mixolimnion, forms carbon film on tungsten film again.In the vacuum deposition apparatus that is proposed in this application case, two vacuum arc evaporation sources have been installed, have been made negative electrode with tungsten and carbon respectively, thereby formation tungsten film and carbon film in substrate have been bombarded in substrate.This invention is not owing to have transition layer between tungsten film and the carbon film, so the bonding force between them still can not reach the ideal level, and, exist directivity owing to carry out plated film by arc-over with tungsten electrode and carbon electrode, be difficult to guarantee the homogeneity and the isotropy of film.
Chinese patent application case 01143088.5 discloses a kind of preparation method of modified non-crystal carbon film by metal iron implantation, this method is to adopt earlier magnetic control sputtering device to deposit the coating of 10～20 μ m on substrate surface, does the target source with metal bar again on metal ion implantation machine and with the high pressure line of 30～200KV metal ion is injected in the coating and goes.This method mainly is that surperficial carbon film performance is made improvement, it is hard to tell that this way of injecting metal ion outside film can fundamentally solve base material with the suitability problem between the carbon film.
Secondly, for big parts and baroque parts, how to guarantee that also there are bigger problem in the homogeneity of film and isotropy.In existing film deposition technique, the group row of carbon film and base material (being parts) all have certain directivity, and form the carbon ion generating unit of DLC film such as ion gun, magnetron sputtering target, cathode arc source etc., realize large-area comprehensive deposition application case 01121264.0 and Chinese patent ZL97103251.3 as the aforementioned, require the carbon ion generating unit necessary enough big on the one hand; Also must make the base material (being parts) that is deposited do complicated rotation on the other hand, this is quite difficult in the finite space of vacuum chamber.
Summary of the invention
Imagination of the present invention is to utilize radio-frequency plasma chemical vapor deposition method depositing diamond-like carbon film on workpiece, considers that the plasma body that is produced by the glow discharge of hydro carbons carbon-source gas surrounds matrix or workpiece, and having good comprehensive property is isotropy; And because radio-frequency plasma chemical vapor deposition method temperature is lower, this helps widening diamond-like carbon film in industrial applicable scope.Through theoretic discussion and experimental study, the inventor seeks a kind of manufacture method of diamond-like carbon film, and has made the parts of various band quasi-diamond coating films with it.
The invention provides a kind of manufacture method of diamond-like carbon film, adopt chemical vapor deposition method, it is characterized in that strengthening chemical vapor deposition method (Ratio frequency Plasma enhanced ChemicalVapor deposition with radio-frequency plasma, be designated hereinafter simply as RFPECVD), at least a portion of substrate, form metal level; On this metal level, form nitride or carbide membrane; On nitride or carbide membrane, form diamond-like carbon film again.
The method that radio-frequency plasma of the present invention strengthens chemical vapour deposition be in substrate, deposit in advance one deck combine with base material good metal level, on this metal level, deposit its nitride film or carbide membrane then successively; Also can deposit one deck nitride film and deposit one deck carbide membrane more thereon; On metal nitride or metallic carbide film, deposit one deck diamond-like carbon film at last.
Have a removable metal sputtering source in the method for the invention at least, can be by it to parts surface sputter and the various metal levels of deposition in vacuum chamber; Inflated with nitrogen or carbonaceous gas are deposited on the metal level of workpiece by radio-frequency plasma and form metal nitride layer (film) or metal carbide layer (film) respectively in the vacuum chamber, close the metal sputtering source at last and extract nitrogen out, only keep methane gas by parameters such as regulating voltage, electric current and methane gas pressure, form the diamond-like carbon film of high adhesive force at workpiece surface.
The said metal level that at first forms in substrate of the present invention is mainly considered the suitability problem of this metal level, promptly requires the bonding force between this metal level and the base material to want big on the one hand; This metal level and its nitride film or carbide membrane also want big with the bonding force between the diamond-like carbon film on the other hand.
The material of the said metal level of the present invention is to adopt metals such as titanium, chromium, zirconium and tungsten.
In the said substrate of the present invention nitride film on sedimentary metal level, the metal level or the thickness of carbide membrane and each layer of diamond-like carbon film (film) be 5～200 nanometers.
Correspondingly the present invention proposes a kind of parts with coating film, it comprises substrate and coating film, it is characterized in that depositing metal level at least a portion of this substrate; On metal level, deposit the nitride film or the carbide membrane of this metal; On metal nitride films or carbide membrane, deposit diamond-like carbon film.
The invention allows for a kind of deposition apparatus of making above-mentioned compound diamond-like carbon film, it comprises vacuum chamber, plasma device, it is characterized in that:
(1) have a removable metal sputtering source in the vacuum chamber at least, vacuum chamber can charge into the gas mixture of the adjustable argon of composition, nitrogen and carbonaceous gas respectively;
(2) excitation process of plasma body is carried out in two different spaces are plasma body generation chamber and plasma processing chamber respectively with plasma-deposited process.
Plasma body of the present invention generates indoor radio-frequency drive coil, intake ducting and the metal sputtering source of being equipped with, and wherein the radio-frequency drive coil is connected with matching box and 13.56MHz high frequency electric source.
Upper and lower battery lead plate, jet system and metal homogeneous net are installed in the plasma processing chamber of the present invention.
Above said energisation mode also can be capacitive coupling.
It can be equipped with the magnetic control coil on every side metal sputtering of the present invention source, like this magnetron sputtering technique is combined with the plasma body chemical vapour deposition technique.
Between two electrodes waveguide can be installed again up and down in the plasma processing chamber of the present invention, the external microwave generator of waveguide, the space that so again the microwave of 2.45KMHz is incorporated into plasma body is come, and the energy by microwave increases the density of plasma body and forms high density plasma.
Compound diamond-like carbon film deposition apparatus of the present invention also can be provided with the vacuum chamber of reload (charging and a discharging) that is communicated with its level in addition on the same horizontal plane of plasma processing chamber, constitute a kind of semicontinuous film coating apparatus.This vacuum chamber is connected to the preliminary vacuum system, and a valve is installed between it is with the plasma body treatment chamber, and this valve is closed usually.When needs reload, earlier refuelling cell is opened, installed the material (promptly desiring the work of plated film) that will change, close refuelling cell and vacuumize, when the indoor vacuum tightness in this chamber (being pressure) when reaching 2Pa, close plasma body and generate the chamber with the high vacuum valve between the plasma body treatment chamber.Open refuelling cell again with the valve between the plasma treatment chamber this moment, just can the workpiece that plate be got back to refuelling cell by being located at the mechanism in the refuelling cell, and will need film-coating workpiece to be placed on the sample table of plasma processing chamber.Close refuelling cell subsequently with the valve between the plasma treatment chamber, when treating that pressure reaches 2Pa in the plasma processing chamber, just can open plasma processing chamber again, begin new workpiece is carried out coating film treatment with the vacuum valve between the plasma body generation chamber.This semicontinuous film coating apparatus of the present invention can greatly be enhanced productivity in actual applications.
Description of drawings
Figure 1 shows that the part viewgraph of cross-section that covers an example of carbon film parts.
Figure 2 shows that the structural representation of an example of plasma CVD device.
Figure 3 shows that Laser Raman spectrogram at the sedimentary carbon film of stainless steel surface.
Figure 4 shows that The friction coefficient was rotated the curve that the number of turns changes when DLC film and steel ball were to mill under the different velocities of rotation.
Figure 5 shows that delineation curve at sedimentary diamond-like carbon film of stainless steel surface and base material.
Figure 6 shows that and possess the PECVD device that plasma body generates chamber and plasma processing chamber.
Figure 7 shows that semi continuous PECVD device.
Figure 8 shows that electron cyclotron wave resonance PECVD device.
Figure 9 shows that atomic force microscope images at bit face plating TiN film and diamond-like carbon film.
In the accompanying drawing: 1 covers the carbon film parts, 2 vacuum chambers, 3 shower pipes, 4 pole plates support, 5 high-frequency electrodes, 6 plasma bodys, 7 matching circuits, 8 high frequency electric sources, 9 reactant gases intake ductings, 10 viewing windows, 11 substrates, 12 titanium films, 13 titanium nitride films, 14 titanium carbonitride films, 15 carbon films (DLC film), 16 vacuum valves, 17 vacuum systems, 18 valves, 19 mass flow controllers, 20 sources of the gas, 21 vacuum leads, 22 heater leads, 23 radio-frequency power supplies lead-in wire, 24 vacuum gauges lead-in wire, 25 plasma processing chamber intake ductings, 26 magnetic valves, 27 direct supplys lead-in wire, 28 radio-frequency coil joints, 29 plasma bodys generate chamber intake ducting, 30 upper end covers, 31 coils, 32,33 targets, 34 uniform gas boards, 35 viewing windows, 36 heater strips, 37 plasma bodys generate chamber, 38 plasma processing chambers, 39 toroidal nozzles, 40 wire nettings, 41 sample table, 42 specimen holders, 43 Sample Rooms, 44 Sample Room doors, 45 magnetic force transmission mechanisms, 46 vacuum leads, 47 viewing windows, 48 reaction chambers, 49 reaction chamber rear flanges, 50 push-pull valves, 51 microwave generators, 52 waveguides, 53 reaction chambers, 54 solenoids, 55 molecular pump pump-lines.
Embodiment
Below in conjunction with accompanying drawing content of the present invention is further described and replenishes.
Because three parts in the content of the present invention: the manufacture method of diamond-like carbon film, the compound diamond-like carbon film deposition apparatus with the parts of compound coating film and this method of enforcement with this method manufacturing is to be mutually related, and they are to belong to same inventive concept.Should not they are separated during specific embodiments of the invention in narration, and should totally be illustrated as one, following embodiment comes to this and constitutes.
Embodiment 1: the compound carbon film of depositing Ti/TiN/TiC/DLC on stainless steel substrates
One covers DLC membrane element 1 and has substrate 11 among Fig. 1, is superimposed upon metallic membrane 12, nitride film 13, carbide membrane 14 and carbon film 15 on substrate 11 at least a portion, and they are deposited in the substrate successively.
Table 1 transition layer preparation technology
Cover the excellent specific property that DLC membrane element 1 has low friction and high-wearing feature, this is because be covered with the DLC film 15 of one deck high rigidity on its surface.Sticking power between sticking power between sticking power between DLC film 15 and the carbide membrane 14, carbide membrane 14 and the nitride film 13, nitride film 13 and metallic membrane 12 and metallic membrane 12 and the substrate 11 is all very big.Therefore, the sticking power of 15 pairs of substrates 11 of DLC film is also very big.Thereby, cover DLC membrane element 1 and can keep its low frictional coefficient and high wear resistance steadily in the long term.
Low and high the covering in the DLC membrane element 1 of wear resistance at frictional coefficient, substrate 11 can be such as class engine components such as cam, valve stem, piston, piston ring, gear, bearings, also can be mechanical parts such as drill bit, milling cutter, cutting tool, mould, can also be components of machine such as razor blade, spectacle frame, medicine equipment.Have covering DLC membrane element 1 and can preferably being used as engine parts, cutting part or the like and requiring parts of this class substrate 11 with low-friction coefficient and high-wearing feature.
Below description is covered the manufacture method of DLC membrane element.DLC film 15 adopts condenser coupling radio frequency plasma body chemical vapor phase growing apparatus to form.The formation that whole film is can be designed to the form of pipelining.
Accompanying drawing shown in Figure 2 is the carbon film-forming appts synoptic diagram of the condenser coupling radio-frequency plasma chemical gaseous phase depositing process of the present invention that adopted, and wherein acetylene gas is a unstripped gas.This carbon film forming device comprises vacuum reaction chamber 2, vaccum-pumping equipment 17, shower pipe 3 and make gas become the device (high-frequency electrode 5 links to each other with high frequency electric source 8 by a matching circuit 7) of plasma body here.Vaccum-pumping equipment 17 can be found time the air in the reaction chamber 2.Shower pipe 3 is introduced carbonaceous gas (being methane or acetylene gas) here and is evacuated in the equipment 17 evacuated reaction chambers 2.The device that makes gas become plasma body will excite by the gases in the shower pipe 3 introducing reaction chambers 2 and become plasma body.High-frequency electrode 5 applies the high-frequency voltage that attracts from high frequency electric source 8 by matching circuit 7.Thus, the gas of introducing reaction chamber 2 forms plasma body, i.e. position shown in the numeral 6 in the drawings.
In carbon film forming device shown in Figure 2, body material 11 is arranged on the high-frequency electrode 5 of reaction chamber 2.When the beginning depositing carbon film, gas (air that for example comprises nitrogen, oxygen isoreactivity gas) is discharged from reaction chamber 2 by vaccum-pumping equipment 17, makes reaction chamber 2 inside become negative pressure state, below 1Pa.After this, rare gas elementes such as argon gas are fed reaction chamber 2 by air feeder 9, make the indoor pressure that reaches 3～5Pa, so just can help keeping of glow discharge.Adopt argon plasma that reaction chamber 2 and body material 11 were carried out pre-washing about 15 minutes.From the acetylene (C of shower pipe 3 introducings as unstripped gas
2H
2) gas, and make and be in ideal film forming pressure state in the reaction chamber 2.Usually, the pressure of 2 li of reaction chambers is 10～100Pa.The high-frequency electrode 5 that is fixed on the body material 11 passes to high-frequency voltage.Then, form methane gas plasma body 6 in reaction chamber 12 the insides, as the carbon laydown of methane component on body material 11.Like this, on body material 11, formed carbon film.
Subsequently, reactant gasess such as acetylene and hydrogen are fed reaction chamber 2 by air feeder 9, keeping reaction chamber 2 pressure, formation DLC film 15 on carbide membrane 14 under the situation of about 10Pa.
In this operation, high frequency electric source 8 adopts the RF power supply unit, and voltage is 500V to 2800V, and frequency is 13.56MHz.In this example, be applied to negative bias in the substrate 11 in the scope of 100V～1000V, in film deposition process, change to low by height by regulating radio-frequency voltage, make the negative bias that is added in the substrate 11.Because the effect of the negative bias that applies in substrate 11, the carbon ion in the plasma body is attracted to substrate 11.Just formed DLC film 15 on the carbide membrane 14 thus.
Adopt aforesaid method to form DLC film 15, can obtain following advantage:
When forming DLC film 15, not specially to substrate heating or cooling, because the effect of plasma body and substrate is estimated underlayer temperature (different with the voltage that is applied) than room temperature height, but usually can be above 150 ℃.
The production method of plasma body adopts radio frequency method, rf electric field adopts capacitive coupling, its outstanding feature is to obtain the big area uniform electric field distribution, this is that the uniform high-quality thin film of preparation property is necessary, and the interaction of plasma body and its surrounding medium is focused near the negative electrode the limited area, promptly deposition and sputter procedure almost all are limited in so just greatly reducing the pollution of reaction chamber wall near the electrode surface at substrate place.
Macroparticle in the plasma body (as dust etc.) repels with the substrate of negative bias mutually because of electronegative, helps forming the high quality dense film of free of pinholes.
Utilize the film quality densification of this method preparation, film has smaller internal stress and good adhesive power;
Equipment and simple to operate is convenient to be designed to automatic assembly line on technology, be easy to promote the use of in industry.
Fig. 3 has shown the Laser Raman spectrogram at the sedimentary carbon film of stainless steel surface.Decomposing spectral resolution by Gauss is that two peaks are D peak and G peak, and wherein the D peak appears at 1315cm
-1The place, the G peak appears at 1520cm
-1The place.This figure is the Raman spectrogram of typical diamond-like carbon film.In the diamond-like carbon film of analysis revealed the present invention preparation, the volume percent of quasi-diamond is more than 20%.
By bolt-dish friction and wear tester the frictional behaviour of the diamond-like carbon film that makes is tested.Select for use the Stainless Steel Ball conduct to the mill body during experiment.Experiment is carried out under room temperature, drying conditions, to doing slip between mill part and the print, and frictional coefficient on-line monitoring continuously in the test.Used load can select 1,2,5 and 10N respectively for use, and velocity of rotation can select 30,60,120,180,240 and 300rpm respectively for use.
Fig. 4 has provided when carrying out DLC film and steel ball to mill under different velocities of rotation The friction coefficient and has rotated the curve that the number of turns changes.The velocity of rotation of two curve representative samples is respectively 30rpm and 300rpm, the initial friction coefficient of sample does not show in the drawings, because these results are that (several milliseconds) are obtained by the monitoring tangential force by the foil gauge on the socle girder and calculate by program in the extremely short time.Measured average friction coefficient is respectively 0.003 and 0.002.The frictional coefficient of institute's test sample product is lower than the report of more previous pertinent literatures.
Utilize scratch test to measure the bonding force of carbon film and substrate.Scratch test is measured by multifunction friction wear testing machine.Pressure head loads on diamond-like carbon film to be measured surface with certain preloading (10g), and behind the loading 10s, with the speed setting in motion of 0.1mm/s, and load evenly is increased to 250g in the distance of 10mm.Output is subjected to force signal, exports acoustic emission signal simultaneously.Judge peeling off of film by detecting acoustic emission signal, experimental data adopts effective result of experiment more than three times.
By scratch test, to understand the bonding strength of diamond-film-like and base material to film.Form the DLC film according to table 2, do the contrast experiment.Measured film (1), film (2), film (4) and film (5) bonding force respectively with base material.Fig. 5 is the delineation curve of film (5) and base material.The acoustic emission signal of output when AE is illustrated in delineation among the figure, Fx represents the frictional force in the delineation process, and Fz is illustrated in the load that puts on film in the delineation process.Along with the increase of load, frictional force also presents linear increasing.When load was increased to certain value, acoustic emission signal was undergone mutation, and sudden change also appears in frictional force simultaneously, and the load of this moment is the critical load value (Lc) that film begins to peel off, and the critical load value of film (5) is 6.0N as shown in Figure 5.According to experimental result, the critical load value of film (1), film (2) and film (4) is respectively 5.4N, 3.8N and 2.8N.Delineation is the result show, the carbon film that four kinds of different condition deposit obtain and the bonding strength of base material have tangible difference.By film (1), film (2) and film (5) more as can be seen, ultimate load increases along with the reduction of deposition voltage.In addition, by the comparison of film (2) and film (4), ((stainless steel/Ti/TiN/DLC) has better bonding force than the compound film system that does not contain TiC for stainless steel/Ti/TiN/TiC/DLC) to comprise the compound film system of TiC as can be seen.
As mentioned above, provided by the invention on stainless steel the manufacture method of depositing diamond-like carbon film, by designed intermediate layer, can be on stainless steel-based piece surface comprehensive big area depositing diamond-like carbon film, this carbon film is to the substrate adhesion height.Manufacturing method according to the invention can effectively form the film of diamond-like carbon film and other type.
Embodiment 2 uses magnetron sputtering in conjunction with the compound carbon film of RFPECVD equipment depositing Ti/TiN/TiC/DLC on stainless steel substrates
On the basis of precedent 1 RFPECVD equipment of the present invention, magnetron sputtering and PECVD equipment are combined, thereby realized on an equipment, realizing depositing diamond-like carbon film and intermediate layer (as metal, nitride, carbide etc.), improved sedimentation effect.
RFPECVD device shown in Figure 6 possesses round tube type plasma body generation chamber 37 (top) and is the plasma processing chamber 38 (bottom) of round tube type equally, forms vacuum chamber (filming chamber) by them.Two Room are in same axis, and two Room connect setting up and down.Plasma body generates chamber 37 and is provided with the RF coil 31 of antenna-like along its outer wall, and matching box that has omitted among coil connectors 28 and the figure and the high frequency electric source (RF power supply) of 13.56MHz link to each other.In plasma processing chamber 38, indoor bottom is provided with the sample table 41 of placing sample, and sample table 41 belows are provided with gas barrier 21.
In addition, plasma body generates and to be connected with gas in the chamber 37 and to enter pipeline 25, it with figure in the gas supply part that omitted divide and link to each other.Insert gas on the position below the interface of plasma body generation chamber 37 and plasma processing chamber 38 omits and entered pipeline 25, one end of inlet tube links to each other with closed circle ring-type jet pipe 39, the other end be arranged in another gas supply part that outdoor figure omitted and divide and link to each other.Gas spray pipe 39 is set on the position in the face of sample, towards the direction of sample table 41 uniformly-spaced to be provided with a plurality of gas squit holes.Between gas spray pipe 39 and sample, be provided with metal homogeneous net 40, to guarantee the uniform distribution of gas.
As required, can utilize the well heater 36 that is contained in the sample table 41 to come print is heated.
Sample table 41 links to each other with the matching box and the high frequency electric source (RF power supply) that have omitted by radio-frequency power supply joint 23, and therefore becoming membrane sample both can be that electro-conductive material also can be semiconductor material or insulating material.
When adopting above-mentioned film deposition system, in plasma processing chamber 38, introduce the film forming gas that the part carbon film forms usefulness, simultaneously the part of remainder being introduced plasma body generates in the chamber 37, the high-frequency induction electric field that the gas of introducing this chamber is formed by the high frequency power that is outputed to joint 28 by high frequency electric source forms the plasma body of being with metal ion, again with this plasma body introducing plasma processing chamber 38.Gas in the plasma decomposes plasma processing chamber 38 of introducing plasma processing chamber 38 forms carbon film on sample.
In addition, can apply high frequency power by this power supply to sample table 41, decompose the gas (formation plasma body) in the plasma processing chamber 38 effectively by suitably selecting the output rating of radio-frequency power supply.So just can control plasma body respectively and generate the plasma body of the gas formation in the chamber 37 and the plasma body that the indoor gas of plasma treatment forms.
Use film deposition system shown in Figure 6, when formation comprises the carbon film of hydrogen and metal etc., hydrocarbon compound gas is introduced in the plasma processing chamber 38, in generating chamber 37, introduces plasma body the sputter gas of formation such as rare gas element, this sputter forms plasma body with gas by the high-frequency induction electric field that the high frequency power that is outputed to joint 28 by high frequency electric source forms, like this plasma body that generates is reached because the sputtering particle that plasma body generates sputtering target 33 sputters is introduced in the plasma processing chamber 38, decompose hydrocarbon compound gas, on article, can form and comprise metal, the carbon film of metallic compound.Certainly, apply high frequency power to sample table 41, also can effectively decompose the gas (formation plasma body) in the plasma processing chamber 38 by the power supply of the suitable output rating of tool.
Prepare the compound carbon film of Ti/TiN/TiC/DLC with this depositing device on metal base such as stainless steel substrates, used reactant gases is argon gas, nitrogen and methane (or other carbon-source gas), target 33 titanium target.The composition of gaseous mixture is controlled by the relative velocity of gas, monitors by magnetic valve 26 and gaseous mass flow director.Ratio by the stepless control reactant gases forms the multilayer transition film, thereby improves the bonding force of film and substrate and improve surface hardness.In the process of deposition transition layer, the variation of the ratio that methane and nitrogen are shared is respectively from zero to 30% and from 30% to zero.It is 70% constant that the shared ratio of argon gas keeps.In the preparation process as for last diamond-like carbon film, improve the ratio of methane gradually, be fixed on certain ratio (as 60%) at last,, can obtain the diamond-like carbon film of different hardness by the last ratio of control methane.
On the basis of the RFPECVD of embodiment 2 equipment, microwave ECR, the coupling of sense formula are combined with plasma generating apparatus, improve sedimentation effect.
RFPECVD device shown in Figure 8, be under the RF power drives, utilize microwave that reactant gases is excited into plasmoid, simultaneously under the contraction of magnetic field constraint space plasma, formed electron cyclotron wave resonance plasma body, reached and quicken film forming purpose.
In this equipment, the energetic ion of utilization under magnetically confined is to effective sputter of target and the chemical reaction under the high ionization level plasma environment, can be at different matrix surface deposition metallic membrane, metal nitride films, metallic carbide film and diamond-like carbon film, can deposit the compound film system of different structure and performance characteristics according to different service requirementss.
This equipment of use deposits the Cr/CrN/CrC/DLC compound film system on razor blade technological process is as follows:
Sample to be plated is placed on the specimen holder.Simultaneously, article are heated to 700-1000 ℃.When temperature rose, it is high that the hardness of coating just becomes, and adamantine ratio increases in the film.
Reaction chamber is evacuated to 1 x 10 by turbomolecular pump and sliding vane rotary pump
-6Holder or lower vacuum tightness.The surface of sample by high-energy electron and nonproductive atom adding with cleaning.Except introducing nonproductive gas, also introduce nitrogen and methane isoreactivity gas by input system.In the deposition process, the pressure of reaction chamber remains on the 0.1-300 holder, for example 10 holders.Owing to have than higher pressure, can the high speed deposition sample and sample extensively is distributed in the reaction chamber.Mode with the microwave-excitation reactant gases is identical with the mode that aforementioned nonproductive gas is carried out.Be deposited on the sample as the form of the last carbon film of the result of hybrid resonance with the DLC film.
Prepare the compound carbon film of Cr/CrN/CrC/DLC with this depositing device on metal base such as razor blade, used reactant gases is argon gas, nitrogen and methane (or other carbon-source gas), target chromium target.Be incorporated into reaction chamber 53 by the gas input system with the flow rate of 30sccm as the argon gas of nonproductive gas, the microwave of 2.45 mega hertzs then is transmitted into reaction chamber 53 from 500 watts microwave generator 51 by waveguide 52, and has stood by solenoid 54 induced magnetic fields in this space.By the energy of microwave, produced highdensity plasma body at reaction chamber 53.In the deposition process, the composition of gaseous mixture is controlled by the relative velocity of gas, monitors by magnetic valve and gaseous mass flow director.Ratio by the stepless control reactant gases forms the multilayer transition film, thereby improves the bonding force of film and substrate and improve surface hardness.In the process of deposition transition layer, the variation of the ratio that methane and nitrogen are shared is respectively from zero to 30% and from 30% to zero.It is 70% constant that the shared ratio of argon gas keeps.In the preparation process as for last diamond-like carbon film, improve the ratio of methane gradually, be fixed on certain ratio (as 60%) at last,, can obtain the diamond-like carbon film of different hardness by the last ratio of control methane.
By the CONTROL PROCESS process, utilize this equipment can deposit different film structures such as Cr/DLC, Cr/CrN/DLC, Cr/CrC/DLC respectively at sample surfaces.
The semicontinuous production unit of embodiment 4 usefulness is at deposition on glass DLC film
On the basis of the RFPECVD equipment in embodiment 1,2,3,, can effectively reduce the pollution of atmospheric environment, realize semicontinuous production print by Sample Room and reaction chamber are kept apart.
In the RFPECVD device shown in Figure 7, outside plasma processing chamber, add a Sample Room 43, the double as discharge chamber, separate with valve 50 between two Room, when valve open, the pallet that loads substrate can enter reaction chamber 48 by Sample Room 43 through piping, and the substrate that deposition is good is sent into loading space 43 by reaction chamber 48 more simultaneously.Valve-off 50, cooling, the substrate new substrate of packing into is taken out in discharging, then Sample Room 43 is vacuumized.Can guarantee that like this reaction chamber is not subjected to topsoil, not only improve plated film efficient but also can guarantee film quality.
Utilize this deposition method on optics such as glass, to prepare nano level diamond-like carbon film as erosion resistant coating, improve the anti-zoned wiping performance of optics such as glasses, improve the work-ing life of such device.
This equipment of use is as follows in the technological process of deposition on glass nano level diamond-like carbon film:
Before the plated film sample by alkali lye deoil, the order of distilled water cleaning, acetone cleaning, ultrasonic cleaning, ethanol dehydration cleans.For the used reactant gases of depositing diamond-like carbon film is argon gas, hydrogen and methane (or other carbon-source gas).During reaction, at first the flow velocity with 5sccm feeds argon gas to reaction chamber, and the power of adjusting radio-frequency power supply is to 100W, and the self-bias of the negative plate at print place is-380V to clean sample surfaces about 5 minutes with argon ion.After cleaning finishes, feed methane and hydrogen respectively to reaction chamber, flow velocity is respectively 10sccm and 30sccm, and the power of adjusting radio-frequency power supply is 1500W, and the self-bias of negative plate is-400V that at sample surfaces depositing diamond-like carbon film, the plated film time selected for use 30 minutes.
Sedimentary DLC film can improve the hardness and the anti-zoned wiping performance of glass print significantly, and to the reciprocal scratching 100 times in its surface, sample surfaces does not have cut with glass point or sapphire.
With ultraviolet-visible spectrophotometer at 190nm～1100nm wavelength region build-in test the transmitance of sample behind the plated film, test result shows that sedimentary DLC film has anti-reflection effect at visible light, region of ultra-red.
Embodiment 5 deposits compound W/WC/DLC film on High Speed Steel Bit and threading tool
With Fig. 6 equipment can the double thread instrument etc. cutter and the compound DLC film of component of machine surface batch deposition as erosion resistant coating, the work-ing life of improving the surface quality of sample and improving sample.
The compound carbon film of preparation W/WC/DLC adopts compound diamond-like carbon film deposition apparatus of the present invention on High Speed Steel Bit, and used reactant gases is argon gas and methane (or other carbon-source gas), and target 33 is used tungsten target.The composition of gaseous mixture is controlled by the relative velocity of gas, monitors by magnetic valve 26 and gaseous mass flow director.Ratio by the stepless control reactant gases forms the multilayer transition film, thereby improves the bonding force of film and substrate and improve surface hardness.In the process of deposition transition layer, the variation of the ratio that methane is shared is to 25% from zero.In the preparation process as for last diamond-like carbon film, improve the ratio of methane gradually, be fixed on certain ratio (as 60%) at last,, can obtain the diamond-like carbon film of different hardness by the last ratio of control methane.
By the CONTROL PROCESS process, utilize this equipment can also deposit different film structures such as Ti/TiN/TiC/DLC in bit face.
Behind above-mentioned process deposits carbon film, the roughness of workpiece surface all obviously descends.(figure a) and the afm image comparison diagram of compound carbon film (figure b) to Figure 9 shows that depositing TiN film on workpiece.The sweep limit of Fig. 9 (a) is 10 μ m*10 μ m, and the sweep limit of Fig. 9 (b) is 5 μ m*5 μ m.From scheming as seen, Fig. 9 (b) is putting on the twice basis than Fig. 9 (a), and is still more smooth, and the compactness of film has also strengthened.
Above-mentioned workpiece is done the performance comparison experiment, and experiment condition is: part to be processed is a stainless material, and cutting speed is 16m/s, feeding speed 0-30mm/rev, blind hole depth 18mm, water cooling.Experimental result shows, deposit compound carbon film after, improved 3-10 the work-ing life of workpiece doubly, the surface topography of work piece also has improvement to a certain degree simultaneously, cutting quality has had raising to a certain degree.
Embodiment 6 DLC films deposited on resin material
Utilize equipment of the present invention on optics such as resin lens, to prepare nano level diamond-like carbon film as erosion resistant coating, improve the anti-zoned wiping performance of resin lens, improve work-ing life.
The technological process of depositing nano level diamond-like carbon film is as follows on resin material:
Before the plated film sample by alkali lye deoil, the order of distilled water cleaning, acetone cleaning, ultrasonic cleaning, ethanol dehydration cleans.Adopt compound diamond-like carbon film deposition apparatus of the present invention, used reactant gases is argon gas, hydrogen and methane (or other carbon-source gas).During reaction, at first the flow velocity with 4sccm feeds argon gas to reaction chamber, and the power of adjusting radio-frequency power supply is to 100W, and the self-bias of the negative plate at print place is-380V to clean sample surfaces about 5 minutes with argon ion.After cleaning finishes, feed methane and hydrogen respectively to reaction chamber, flow velocity is respectively 10sccm and 30sccm, and the power of adjusting radio-frequency power supply is 1500W, and the self-bias of negative plate is-400V, at sample surfaces depositing diamond-like carbon film.
Sedimentary DLC film can improve the hardness and the anti-zoned wiping performance of glass print significantly, uses the reciprocal scratching of BH pencil 50 times, and sample surfaces does not have cut.
Claims (7)
1, a kind of diamond-like carbon film manufacturing method, utilize mainly by vacuum chamber, plasma body generates the diamond-like carbon film deposition apparatus of chamber and plasma processing chamber formation, make diamond-like carbon film, be to strengthen chemical vapour deposition in conjunction with magnetron sputtering technique with radio-frequency plasma, forming material in substrate is titanium, chromium, on this metal level, form nitride or carbide membrane after the metal level of tungsten or zirconium, on nitride or carbide membrane, form diamond-like carbon film again, it is characterized in that by at same diamond-like carbon film deposition apparatus, in substrate, form metal level, nitride or carbide membrane and diamond-like carbon film.
2, a kind of deposition apparatus of implementing the described diamond-like carbon film manufacturing method employing of claim 1, it comprises that vacuum chamber, plasma body generate chamber and plasma processing chamber, it is characterized in that: have the metal sputtering source that to change in the vacuum chamber at least, can charge into argon, nitrogen and carbonaceous gas respectively in the vacuum chamber, the composition of the mixed gas that the three constitutes can be regulated.
3, the deposition apparatus that adopts by the described diamond-like carbon film manufacturing method of claim 2, it is characterized in that said plasma body generates indoor radio-frequency drive coil, intake ducting and the metal sputtering source of being equipped with, wherein radio-frequency coil is connected with the high frequency electric source of matching box and 13.56MHz.
4, the deposition apparatus that adopts by the described diamond-like carbon film manufacturing method of claim 2 is characterized in that said plasma processing chamber is equipped with upper and lower battery lead plate, jet system and metal homogeneous net.
5, the deposition apparatus that adopts by the described diamond-like carbon film manufacturing method of claim 2 is characterized in that around the said metal sputtering source magnetic control coil being installed.
6, the deposition apparatus that adopts by the described diamond-like carbon film manufacturing method of claim 2 is characterized in that installing between upper and lower two battery lead plates of said plasma processing chamber the waveguide of external microwave generator.
7, the deposition apparatus that adopts by the described diamond-like carbon film manufacturing method of claim 2 is characterized in that being provided with in addition a vacuum chamber that reloads that is communicated with its level on the same horizontal plane of plasma processing chamber.
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