CN103173731B - Method for improving property of TiN/TiCN multi-layer composite film material - Google Patents
Method for improving property of TiN/TiCN multi-layer composite film material Download PDFInfo
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- CN103173731B CN103173731B CN201110439964.2A CN201110439964A CN103173731B CN 103173731 B CN103173731 B CN 103173731B CN 201110439964 A CN201110439964 A CN 201110439964A CN 103173731 B CN103173731 B CN 103173731B
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Abstract
The invention discloses a method for improving property of a TiN/TiCN multi-layer composite film material. According to the method, nitrogen plasma bombardment is performed on a TiN/TiCN multi-layer composite film, and the mechanical property of the treated TiN/TiCN multi-layer composite film is not changed obviously. However, the stress of the whole film is improved, and the friction coefficient and wear rate of the internal TiN layer are obviously reduced.
Description
Technical field
The present invention relates to a kind of method utilizing nitrogen plasma to improve TiN/TiCN multi-layer compound film material friction performance.
Background technology
TiN and TiCN thin-film material, owing to all having high hardness, excellent to resistance to wear and characteristic that corrodibility, fabulous chemical stability and good electroconductibility and thermal conductivity etc. are excellent, is therefore with a wide range of applications in fields such as machinery, tribology, protection against corrosion, aerospace.TiN/TiCN MULTILAYER COMPOSITE mould material, except combining the advantage of the two, is controlled and dislocation effect by layer thickness, TiN/TiCN multi-layer compound film material internal stress aspect is greatly improved, and its thickness and bonding force is all significantly increased.
At present, physical gas phase deposition technology is one of main method of preparation TiN/TiCN multi-layer compound film material, widely uses in the industry.But the TiN/TiCN multi-layer compound film material directly obtained by these deposition techniques has an obvious defect, and namely TiN layer produces higher frictional coefficient and larger noise when metal to-metal contact.This not only can reduce the work-ing life of TiN/TiCN multi-layer compound film, and can limit its use in more areas, as cutter, gear, bearing etc.
Summary of the invention
Main purpose of the present invention is the tribological property utilizing nitrogen plasma to improve TiN/TiCN multi-layer compound film material.
Adopt nitrogen plasma to improve a method for TiN/TiCN multi-layer compound film material friction performance, its hardness of the film that the method process obtains is constant, and stress reduces, and the frictional coefficient of TiN layer occurs that significantly decline and overall wear resistance improve.
The film that the present invention adopts is the TiN/TiCN multi-layer compound film material prepared according to the preparation method (201110425176.8) of patent super thick TiN-TiCN multi-layer compound film material.Concrete steps are:
A, in deposition process, adopts DC magnetron sputtering system equipment;
Monocrystalline silicon piece or steel disc are fixed on underboarding as base material by B, then underboarding are loaded in deposition chambers, vacuumize; Vacuum tightness when sediment chamber reaches 8.0 × 10
-4-6.0 × 10
-4during Pa, logical argon gas in sediment chamber, dutycycle be 60-80%, pulse direct current negative bias carries out sputter clean base material 10-20min with argon (Ar) plasma body under being the condition of 800-1100V;
C is 20-40sccm at argon flow amount, the distance of target and substrate is 10-15cm, initial cavity chambers temp is at 30-40 DEG C, galvanic current is 2-4sccm, under dutycycle and negative bias are respectively the condition of 60-80% and 0-100V, regulate nitrogen and methane flow by gradual change, sputter pure titanium target, obtained TiN-TiCN multi-layer compound film, depositing time is 100-260min;
After D deposition terminates, chamber temp is 125-135 DEG C, when waiting for chamber temp cool to room temperature, takes out monocrystalline silicon piece or steel disc.
Principle of the present invention: nitrogen is under strong negative bias effect, and orientation produces high-octane nitrogen plasma.Unstable glassy structure is easy to be converted into stable crystalline state and amorphous structure under the energy bombardment of plasma body.Because TiCN layer and TiN layer also exist the concentration difference of stress-difference and decolorizing carbon, tiny decolorizing carbon is caused to shift from TiCN layer to TiN layer in the transmittance process of bombardment energy.The decolorizing carbon of diffusion plays friction-reducing and antiwear action in TiN layer.
A kind of method improving TiN/TiCN multi-layer compound film material property, it is characterized in that in nitrogen atmosphere, the grid bias power supply that application is installed in DC magnetron sputtering device produces plasma body, TiN-TiCN multi-layer compound film is bombarded, reach the object of improving SNR, concrete operation step is:
A is in deposition process, and produced by Shenyang scientific instrument company limited of the Chinese Academy of Sciences with DC magnetron sputtering system equipment, its model is JS-650; Equipment primarily of deposition chambers, carry target plate, underboarding, direct supply, grid bias power supply and pumping system composition, wherein carry target plate and underboarding is vis-a-vis, direct supply is connected on year target plate, and grid bias power supply is connected to underboarding;
B is 90-130sccm at nitrogen flow, the distance of target and substrate is 10-15cm, dutycycle and negative bias produce high-octane nitrogen plasma bombardment TiN/TiCN multi-layer compound film under being respectively the condition of 60-80% and 1000-1200V, the nitriding treatment time is 10-40min;
After C process terminates, chamber temp reduces with the increase of nitriding treatment time, and its scope is at 80-50 DEG C.When chamber temp cool to room temperature, take out TiN-TiCN multi-layer compound film.
Through the Performance comparision of TiN/TiCN multi-layer compound film material and untreated TiN/TiCN multi-layer compound film material process:
Film after process has less stress; The hardness of the film after process is almost unchanged; Untreated film take silicon nitride ball as antithesis, in atmospheric environment, load is 1N, rotating speed is 600rpm and one way coasting distance is under the friction condition of 5mm, when running to 230min (namely touching TiN layer), frictional coefficient rises to about 0.7 from original 0.15, and sends larger noise.And process after film under the same conditions, slide 600min (touching TiN layer already), frictional coefficient maintains about 0.15 always, and does not have noise.
The reason that the present invention has above-mentioned performance is: produce high-octane nitrogen plasma bombardment film by negative bias, cause TiCN layer to be converted into stable amorphous and columnar crystal structure from the glassy structure of instability.Meanwhile, because the tiny decolorizing carbon of induction spreads to TiN layer by the existence of energy difference, concentration difference and stress-difference, and decolorizing carbon is present in TiN layer and will be conducive to reducing the frictional coefficient of TiN layer and extend friction durability of whole film.
Embodiment
In order to understand the present invention better, be described by example.
Embodiment 1:
Deposition: argon gas, nitrogen and methane blended gas are passed in reaction chamber, be adjusted to 1-5 ° retaining flapper valve (control chamber pressure), the distance of target and substrate is 10cm, dutycycle is the negative bias 100V of 80%, initial chamber temp opens direct supply (electric current is 4A) under remaining on the condition of 40 DEG C, sputter pure titanium target, nitrogen and methane flow is regulated by gradual change, total depositing time is 100min, obtains the TiN/TiCN multi-layer compound film that the bimolecular number of plies is 10.Nitriding treatment: stop passing into of argon gas, methane, close direct supply, the distance and the dutycycle that retain flapper valve, target and substrate all remain unchanged, when being 100sccm the Flow-rate adjustment of nitrogen, negative bias being increased to 1100V causes nitrogen to become high-octane plasma bombardment at film surface, and the treatment time is 40min.
Utilize field emission scanning electron microscope (FESEM) to observe thin-membrane section to find, film thickness is 9.9 μm, and TiCN layer is decolorizing carbon bag columnar crystal structure, and TiN layer is columnar crystal structure presss from both sides a small amount of decolorizing carbon, and whole membrane structure is fine and close, is combined well with base material.The existence of these phases is confirmed by high-resolution-ration transmission electric-lens.The stress that the method (i.e. Stoney equation) of fired basis bending tablet calculates film is about 0.52GPa.Show according to nanometer micro-indentation test, the consistency and elasticity modulus of this film is respectively 21.06-37.48GPa and 317.7-345.2GPa.Use UMT friction wear testing machine, load is 1N, and run 600min, its average friction coefficient is 0.15, and wear rate is 4.8 × 10
-7mm
3/ Nm, wearing depth is 2.6 μm, and by worn out for first TiN layer, but frictional coefficient there is no obvious surge in this process, maintains about 0.15 always.
Embodiment 2:
As described in Example 1, the treatment time will change to 20min, obtain the TiN/TiCN multi-layer compound film after processing.
Utilize field emission scanning electron microscope (FESEM) to observe thin-membrane section to find, film thickness is 9.9 μm, and TiCN layer is decolorizing carbon bag columnar crystal structure, and TiN layer is columnar crystal structure, and whole membrane structure is fine and close, is combined well with base material.The existence of these phases is confirmed by high-resolution-ration transmission electric-lens.The stress that the method (i.e. Stoney equation) of fired basis bending tablet calculates film is about 0.79GPa.Show according to nanometer micro-indentation test, the consistency and elasticity modulus of this film is respectively 23.46-27.84GPa and 314.7-334.2GPa.Investigate its friction and wear behavior with UMT friction wear testing machine, experiment condition is as follows: load is 1N, and run 230min, frictional coefficient skips to about 0.65 from original about 0.15, and sends larger noise.
Embodiment 3:
As described in Example 1, directly untreated TiN/TiCN multi-layer compound film is investigated.
Utilize field emission scanning electron microscope (FESEM) to observe thin-membrane section to find, film thickness is 9.9 μm, and TiCN layer is unstable glassy structure, and TiN layer is columnar crystal structure, and whole membrane structure is fine and close, is combined well with base material.The existence of these structures is confirmed by high-resolution-ration transmission electric-lens.Equally, the stress calculating film is about 1.47GPa.Show according to nanometer micro-indentation test, the consistency and elasticity modulus of this film is respectively 23.82-30.07GPa and 328.3-389.2GPa.Investigate its friction and wear behavior under the same conditions, its frictional coefficient skips to about 0.7 from original about 0.15, and sends larger noise.
Claims (1)
1. one kind is improved the method for TiN/TiCN multi-layer compound film material property, it is characterized in that in nitrogen atmosphere, the grid bias power supply that application is installed in DC magnetron sputtering device produces plasma body, TiN-TiCN multi-layer compound film is bombarded, reach the object of improving SNR, concrete operation step is:
A is in deposition process, and produced by Shenyang scientific instrument company limited of the Chinese Academy of Sciences with DC magnetron sputtering system equipment, its model is JS-650; Equipment primarily of deposition chambers, carry target plate, underboarding, direct supply, grid bias power supply and pumping system composition, wherein carry target plate and underboarding is vis-a-vis, direct supply is connected on year target plate, and grid bias power supply is connected to underboarding;
B is 90-130sccm at nitrogen flow, the distance of target and substrate is 10-15cm, dutycycle and negative bias produce high-octane nitrogen plasma bombardment TiN/TiCN multi-layer compound film under being respectively the condition of 60-80% and 1000-1200V, the nitriding treatment time is 10-40min;
After C process terminates, chamber temp reduces with the increase of nitriding treatment time, and its scope, at 80-50 DEG C, when chamber temp cool to room temperature, takes out TiN-TiCN multi-layer compound film.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610765A (en) * | 2001-11-28 | 2005-04-27 | Eppra公司 | Improved method for coating a support with a material |
| CN102230154A (en) * | 2011-06-14 | 2011-11-02 | 上海巴耳思新材料科技有限公司 | Technological process of physical vapor deposition coating |
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| KR0164149B1 (en) * | 1995-03-28 | 1999-02-01 | 김주용 | Method of improving ticn layer |
| US20100203339A1 (en) * | 2009-02-06 | 2010-08-12 | Osman Eryilmaz | Plasma treatment of carbon-based materials and coatings for improved friction and wear properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610765A (en) * | 2001-11-28 | 2005-04-27 | Eppra公司 | Improved method for coating a support with a material |
| CN102230154A (en) * | 2011-06-14 | 2011-11-02 | 上海巴耳思新材料科技有限公司 | Technological process of physical vapor deposition coating |
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