CN106011794A - Preparation method for super-lubricity nanocrystalline-amorphous carbon film in atmosphere environment - Google Patents

Preparation method for super-lubricity nanocrystalline-amorphous carbon film in atmosphere environment Download PDF

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CN106011794A
CN106011794A CN201610371967.XA CN201610371967A CN106011794A CN 106011794 A CN106011794 A CN 106011794A CN 201610371967 A CN201610371967 A CN 201610371967A CN 106011794 A CN106011794 A CN 106011794A
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nanocrystalline
methane
film
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CN106011794B (en
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张俊彦
曹忠跃
强力
张斌
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/503—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using dc or ac discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/272—Diamond only using DC, AC or RF discharges

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Abstract

The invention discloses a preparation method for a super-lubricity nanocrystalline-amorphous carbon film in the atmosphere environment. The preparation method includes the following steps that a pre-cleaned silicon chip is put into acetone and ethyl alcohol to be subjected to ultrasonic cleaning, and then transferred to a substrate plate on the lower portion of a vacuum cavity of plasma enhanced chemical vapor deposition equipment, and the substrate plate is connected with a negative grid bias power supply; vacuumizing is carried out until the vacuum degree is smaller than 1.0*10<3> Pa; argon is introduced, and plasma cleaning is carried out under the condition of direct current bias of 500-800 V so that residual impurities and pollutants on the surface can be removed; methane and nitrogen are introduced, and film coating is carried out for 20-40 min under the condition of direct current bias of 780-820 V; and methane and hydrogen are introduced, and film coating is carried out for 90-120 min under the condition of direct current bias of 780-820 V. The film obtained through the method has nanocrystalline-amorphous characteristics, high hardness and elasticity and excellent frictional performance (the friction coefficient can be continuously kept at about 0.005, and the abrasion rate reaches the grade of -10<17> m<3>/N/m).

Description

The preparation method of superslide nanocrystalline and amorphous C film under atmospheric environment
Technical field
The present invention relates to the preparation side of a kind of nanocrystalline and amorphous C film showing superslide behavior under atmospheric environment Method.
Background technology
Friction and wear is one of major way causing energy dissipation and the inefficacy of mutual moving component in mechanical system.According to Estimate, friction the energy expenditure caused accounts for 1/3rd of global energy resource, there are about the mechanical material loss of 60% simultaneously It is attributed to abrasion.Design has the mechanical system of ultralow friction coefficient and abrasion and sets up superslide system to farthest saving In the energy, minimizing mechanical system, harmful substance has epoch-making meaning to the discharge of atmospheric environment, will produce revolutionary Economic and social benefit.Up to the present, the realization of superslide is concentrated mainly in the experiment that some are relevant to stratified material, such as two Molybdenum sulfide (MoS2), highly oriented pyrolytic graphite (HOPG) and multi-walled carbon nano-tubes (MWCNT), these superslides are mainly due to two Non-commensurability contact between nanometer or micro-meter scale crystal face, needs fine vacuum and superelevation clean environment.On a macroscopic scale, Fault of construction and distortion are the wide gaps that material list reveals that superslide characteristic is difficult to cross.Therefore, explore macroscopic view superslide system to become One of hot subject of scientific and technical personnel's research.
At present, the typical material being hopeful most to be capable of macroscopic view superslide behavior is containing hydrogen diamond membrane (diamond-like carbon, DLC).Owing to the dangling bond of its smooth surface is saturated by hydrogen, passivation, without chemistry between slip surface Physical interaction, it all can show superslide behavior under vacuum and special atmosphere.But its internal stress height, frictional behaviour are by ring Border impact limits more greatly its engineer applied, is especially difficult to superslide under relatively large contacting stress and atmospheric environment.Therefore, Some new technology and methods need to be developed to strengthen the mechanical performance of C film and its tribological property under atmospheric environment, make It also can show superslide characteristic in terms of engineer applied.
Summary of the invention
It is an object of the invention to provide the preparation method of superslide nanocrystalline and amorphous C film under a kind of atmospheric environment.
Using plasma of the present invention strengthens chemical vapour deposition technique and introduces Nano diamond in amorphous carbon grid Granule (less than 10 nm), thus discharge the internal stress of thin film, the mechanical performance of strengthening thin film, it is embedded in amorphous carbon network simultaneously In nano-particle can promote that Bulbus Allii Cepae carbon structure (similar Fuller olefin structure) transfer membrane, in the formation of frictional interface, thus gives thin Film superslide behavior.Based on this thinking, we prepared a kind of and conventional diamond-like carbon film structure different nanocrystalline- Amorphous carbon film.This thin film shows higher hardness (~ 18.94GPa), elastic restitution coefficient (~ 84%) and in atmospheric environment Under ultralow coefficient of friction (~ 0.005) and abrasion (~ 10-17m3/ N/m).The method has gas-phase deposition system technical maturity, sets Standby simple, depositing temperature is low, film forming is uniform, the feature such as reproducible.Before this has greatly widened the application that carbon-base film is potential Scape, the application for carbon-base film provides a kind of new possibility, will promote the technological innovation of component of machine and equipment, favorably Energy conservation type, friendly environment society is built in China.
The preparation method of superslide nanocrystalline and amorphous C film under atmospheric environment, it is characterised in that this preparation method include with Lower step:
1) silicon chip after precleaning is put into ultrasonic cleaning in acetone, ethanol, be then transferred to PECVD On the vacuum chamber lower base dish of depositing device, substrate disk is connected with back bias voltage power supply；
2) evacuation is until less than 1.0 × 10-3Handkerchief；
3) it is passed through argon, under the conditions of Dc bias 500 ~ 800 V, carries out plasma clean, in order to remove the miscellaneous of remained on surface Matter and pollutant；
4) methane and nitrogen it are passed through, plated film 20 ~ 40 minutes under the conditions of Dc bias 780 ~ 820 V；It is passed through methane and hydrogen, Dc bias is plated film 90 ~ 120 minutes under the conditions of 780 ~ 820V.
Described power supply is DC source.
The flow-rate ratio of described methane and nitrogen is 0.8:1.0 ~ 1.2:1.0；The flow-rate ratio of described methane and hydrogen is 1:1.8 ~1:2.2。
The thin film that the present invention is obtained has in nanocrystalline and amorphous feature, i.e. thin film and (is less than containing diamond nano-particles 10nm)；This kind of thin film has higher consistency and elasticity, and its nano hardness is 18.94 GPa, and elastic restitution coefficient is 84%；Institute The nanocrystalline and amorphous C film obtained has the tribological property of excellence, (relative humidity is 20%) and contact stress in atmosphere When reaching 2.89GPa, coefficient of friction is sustainable maintains about 0.005.
The preparation method of the present invention is simple, introduces in vacuum chamber by methane and hydrogen gas, luring at DC source Lead lower generation ionization, be allowed to produce the plasma atmosphere with various groups such as electronics, ion, free radicals, wherein positively charged Various carbon-containing group (CH3 +, CH2 +Deng) under the effect of back bias voltage, do accelerated motion, and formation of deposits thin film in substrate.
Thin film prepared in the present invention infrared spectrum (FTIR), x-ray photoelectron spectroscopy (XPS), X-ray have been carried out Diffraction (XRD) and transmission electron microscope (TEM) etc. characterize.Result shows, this thin film is the carbon containing diamond nano-particles Hydrogen thin film, has nanocrystalline and amorphous architectural feature.
Accompanying drawing explanation
The high-resolution-ration transmission electric-lens figure (HRTEM) of Fig. 1: (A) nanocrystalline and amorphous carbon film；(B) nanocrystalline and amorphous carbon film and The XRD datagram of amorphous carbon-film.
Fig. 2: (A) nanocrystalline and amorphous thin film (FTIR) infrared spectrogram；(B) nanocrystalline and amorphous carbon film and amorphous carbon The C1s Momentum profiles figure of film.
Detailed description of the invention
In order to be better understood from the present invention, illustrated by example.
Embodiment 1
First select the silicon chip three of any surface finish, put it into ultrasonic cleaning in acetone, ethanol, take out silicon chip, use ear washing bulb Proceed to it rapidly after drying up, in the vacuum chamber of plasma enhanced chemical vapor deposition equipment, be placed on substrate disk, start Evacuation.Treat that vacuum is extracted into less than 1.0 × 10-3During handkerchief, being passed through argon, adjusting air pressure is 6.0 handkerchiefs, DC voltage 800 volts In the case of, carry out plasma clean.After cleaning completes, it is passed through methane and nitrogen (flow-rate ratio is 1.0), in Dc bias Depositing thin film under conditions of 800 volts, sedimentation time is 0.5 hour；It is passed through methane and hydrogen (flow-rate ratio is 1.0:2.0), Depositing thin film under conditions of Dc bias 800 volts, sedimentation time is 1.5 hours.
Embodiment 2
At 2800 cm in FTIR spectrogram-1～3000 cm-1In the range of the eigen vibration absworption peak of methyl and methylene occurs, Show that the diamond-like carbon film obtained is hydrogeneous.X-ray photoelectron spectroscopic analysis finds that the combination of thin film C1s can want the highest In conventional diamond like carbon film, show the sp in thin film3Carbon content is higher.It is excellent that reciprocating friction test result indicate that thin film has Different tribological property, in air (relative humidity is 20%), when contact stress is 2.89 GPa, the sustainable dimension of its coefficient of friction Hold about 0.005.

Claims (3)

1. the preparation method of superslide nanocrystalline and amorphous C film under atmospheric environment, it is characterised in that this preparation method includes following Step:
1) silicon chip after precleaning is put into ultrasonic cleaning in acetone, ethanol, be then transferred to PECVD On the vacuum chamber lower base dish of depositing device, substrate disk is connected with back bias voltage power supply；
2) evacuation is until less than 1.0 × 10-3Handkerchief；
3) it is passed through argon, under the conditions of Dc bias 500 ~ 800 V, carries out plasma clean；
4) methane and nitrogen it are passed through, plated film 20 ~ 40 minutes under the conditions of Dc bias 780 ~ 820 V；It is passed through methane and hydrogen, Dc bias is plated film 90 ~ 120 minutes under the conditions of 780 ~ 820V.
2. preparation method as claimed in claim 1, it is characterised in that described power supply is DC source.
3. preparation method as claimed in claim 1, it is characterised in that the flow-rate ratio of described methane and nitrogen be 0.8:1.0 ~ 1.2:1.0；The flow-rate ratio of described methane and hydrogen is 1:1.8 ~ 1:2.2.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109750271A (en) * 2019-02-27 2019-05-14 中国科学院兰州化学物理研究所 A kind of heat resistant and wear resistant damage vibrating screen ball and preparation method thereof
WO2019119646A1 (en) * 2017-12-21 2019-06-27 中国科学院兰州化学物理研究所 Method for improving binding force and tribological property of fullerene-like thin film
CN111074207A (en) * 2019-12-25 2020-04-28 中国科学院兰州化学物理研究所 Preparation method of macroscopic ultra-smooth silver nitrate composite carbon-based film
CN114001142A (en) * 2021-10-26 2022-02-01 东风商用车有限公司 High-load gear with low transmission noise and preparation method thereof

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US20100209665A1 (en) * 2005-09-29 2010-08-19 Konovalov Valeriy V Ultra smooth nanostructured diamond films and compositions and methods for producing same

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CHENGBING WANG等: "Nanocrystalline diamond embedded in hydrogenated fullerenelike carbon films", 《JOURNAL OF APPLIED PHYSICS》 *
JUNYING HAO等: "Influence of flow ratio on mechanical and tribological properties of hydrogenated carbon nitride films prepared by DC-RF-PECVD", 《JOURNAL OF PHYSICS D: APPLIED PHYSICS》 *
WILHELM KULISCH等: "On the growth mechanisms of nanocrystalline diamond films", 《PHYS.STAT.SOL.》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019119646A1 (en) * 2017-12-21 2019-06-27 中国科学院兰州化学物理研究所 Method for improving binding force and tribological property of fullerene-like thin film
CN109750271A (en) * 2019-02-27 2019-05-14 中国科学院兰州化学物理研究所 A kind of heat resistant and wear resistant damage vibrating screen ball and preparation method thereof
CN111074207A (en) * 2019-12-25 2020-04-28 中国科学院兰州化学物理研究所 Preparation method of macroscopic ultra-smooth silver nitrate composite carbon-based film
CN114001142A (en) * 2021-10-26 2022-02-01 东风商用车有限公司 High-load gear with low transmission noise and preparation method thereof
CN114001142B (en) * 2021-10-26 2024-01-02 东风商用车有限公司 High-load gear with low transmission noise and preparation method thereof

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