CN104278241B - A kind of technology of preparing of the thin-film material with multi-environment adaptability - Google Patents

A kind of technology of preparing of the thin-film material with multi-environment adaptability Download PDF

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CN104278241B
CN104278241B CN201310273979.5A CN201310273979A CN104278241B CN 104278241 B CN104278241 B CN 104278241B CN 201310273979 A CN201310273979 A CN 201310273979A CN 104278241 B CN104278241 B CN 104278241B
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film
technology
preparing
gas
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CN104278241A (en
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陈建敏
吴艳霞
吉利
李红轩
冶银平
周惠娣
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Lanzhou Institute of Chemical Physics LICP of CAS
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0073—Reactive sputtering by exposing the substrates to reactive gases intermittently
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides

Abstract

The present invention discloses a kind of molybdenum disulfide with multi-environment adaptability/technology of preparing containing hydrogen amorphous multilayered film material.Using MoS2/a‑C:The design of H sandwich constructions, and prepared using non-balance magnetically controlled sputter technology is reacted.Preparation method is easy, and the membrane structure prepared is fine and close, it is to avoid run through the cavity blemish of film layer；While hard a C:H film layers improve the bearing capacity of film, soft MoS2Film layer improves the greasy property of film, so as to improve the multi-environment adaptability of film.MoS2/a‑C:H plural layers are respectively provided with good tribological property in vacuum, air, nitrogen environment, may be used as space lubriation material and are applied in various fields such as manned space flight airship, interstellar probe, artificial satellites.

Description

A kind of technology of preparing of the thin-film material with multi-environment adaptability
Technical field
The composite lubricating film with multi-environment adaptability is prepared the present invention relates to a kind of utilization non-balance magnetically controlled sputter technology Technology of preparing.
Background technology
The development of the space high-tech industry such as the manned astro-engineering, spacelab, interstellar probe, is that China's economy is built If, national security and development in science and technology be made that positive contribution.One of important feature of space environment is exactly high vacuum, in this environment Under, the oxide-film of metal surface is removed quickly in friction process, is easily adhered between clean metallic surfaces, or even cold Weldering, causes friction pair to be unable to relative motion, this is fatal for space mechanical moving components.In addition, conventional grease lubrication Agent occurs evaporation, decomposition or crosslinking and failed under harsh vacuum environment, easily.So, space technology critical moving components exist Lubrication failure in vacuum environment has become restriction space technology service life of equipment and the bottleneck of reliability, therefore, and development is adapted to The lubriation material and technology of high reliability, extra long life in high vacuum are significant.
Solid lubricant due to having the advantages that low evaporation rate, it is wider temperature range, radioresistance, corrosion-resistant, be Preferable vacuum lubriation material.Thin-film material is significant as the wear-resisting lubricating layer of precise part, and soft metal is due to valency Lattice are expensive and are very limited, and more extensive molybdenum disulfide is used at present（MoS2）Although there is good tribology in vacuum Performance, but storing process has been oxidized but frictional behaviour variation in atmosphere, and corrosion resistant performance is poor in addition, and film hardness is low, easily Producing abrasive dust causes pollution.And new hydrogeneous amorphous carbon-film (a-C:H) although having high rigidity, low-friction coefficient, high abrasion Property, good chemical stability etc., but wear-out life is short under vacuum conditions, significantly limit it in space field should With.
The content of the invention
It is an object of the invention to provide a kind of technology of preparing of the thin-film material with multi-environment adaptability.
The purpose of the present invention can be achieved through the following technical solutions：
The present invention uses MoS2/a-C:The design of H sandwich constructions, and prepared using non-balance magnetically controlled sputter technology is reacted.
A kind of technology of preparing of the thin-film material with multi-environment adaptability, it is characterised in that the preparation process of thin-film material It is to be completed in the vacuum chamber of a non-balance magnetically controlled sputter coating machine, concretely comprises the following steps：
A, activation cleaning surface：Smooth, clean metallic substrates are placed in the vacuum chamber of non-balance magnetically controlled sputter coating machine 10 are evacuated to behind interior-3 Below Pa, is passed through argon gas as ionization of gas, substrate applies pulsed bias, glow discharge generation etc. Gas ions, plasma-activated cleaning is carried out to substrate surface；
It is prepared by B, transition zone：After cleaning is finished, silicon transition zone is prepared first using the method for non-balance magnetically controlled sputter, is selected HIGH-PURITY SILICON is as sputtering target material, using argon gas as sputter gas, matrix extra-pulse back bias voltage, is closed after deposition certain thickness；
C, the method preparation MoS using unbalanced reactive magnetron sputtering2/a-C:H multilayered film materials：Sputtering target material is selected MoS2Target and graphite target, wherein preparing every layer of MoS2Layer and a-C:Reactant gas source at H layers is respectively：Ar and Ar/CH4, by changing Become target current and CH4Be passed through the time, realize MoS2/a-C:H sandwich constructions alternating and mechanical periodicity, open intermediate frequency power supply and arteries and veins Grid bias power supply, depositional coating are rushed, plated film is cooled to temperature less than 40 DEG C after finishing, release vacuum takes out obtained thin-film material.
In step, metallic substrates are selected from stainless steel, steel or titanium alloy.
In step, plasma-activated process parameters range is：The Pa of air pressure 0.2~3.0, pulsed bias -100~- 1200V。
In stepb, transition zone preparation technology parameter scope is：Cavity 0.2~1.0Pa of air pressure, sputtering current 1~12 A, pulsed bias -50~-1000V, the nm of transition region thickness 30~500.
In step C, process parameters range is：Cavity air pressure 0.2~2.0Pa, Ar/CH4Volumetric flow of gas compares 6：1~ 1：6, pulsed bias -100~-1000V, the A of sputtering current 1~25, modulation period is 5~1000 nm.
Coating section microstructure prepared by the present invention is as shown in figure 1, form MoS2/a-C:H nanometer multilayers are alternately tied Structure, in MoS2/a-C:In H multi-layer film structures：Hard a-C:H films provide bearing capacity, soft MoS2Film provides lubricity.Soft formation MoS2Film has good shear action on surface so that the hard formation a-C of sub-surface:H films produce certain journey in low-shearing force level On degree " relative to slide ", alleviate the interfacial stress of high rigidity film layer and maintain toughness；The presence at multiphase fine grain interface, increase The toughness of film, prevents the extension of crackle, and then improve the friction durability of film.
MoS prepared by the present invention2/a-C:H multilayer films and pure MoS2Film and pure a-C:H films are compared：Three kinds of films are distinguished Frictional experiment is carried out in vacuum, nitrogen and air.As a result show, pure MoS2Coefficient of friction is high in atmosphere for film, rubs the longevity Life is short；Pure a-C:Although coefficient of friction is very low in a vacuum for H films, wear-out life is extremely short；And MoS2/a-C:H multilayer films are more Plant and be respectively provided with very low coefficient of friction and very long friction durability under environment.
Plural layers prepared by the present invention can be as space lubriation material in manned space flight airship, star detector, people Make on the movement of metallic part in the fields such as satellite.
The product main performance index of the present invention is as shown in table 1：
Table 1
Brief description of the drawings
Fig. 1 is MoS2/a-C:The profile scanning Electronic Speculum shape appearance figure of H plural layers.
Embodiment
Embodiment 1：Non-balance magnetically controlled sputter coating machine
A. surface is cleaned in activation：Smooth, clean stainless steel plate planar substrates are placed in non-balance magnetically controlled sputter coating machine Vacuum cavity in after, air pressure in vacuum chamber is evacuated to 6 × 10-3Below Pa, it is 2.5 Pa to be passed through high-purity argon gas to air pressure.Beat Pulsed bias power supply is opened, regulation voltage level is -600 V, carries out the min of argon plasma Bombardment and cleaning 25.
B. silicon transition zone is deposited：Argon flow amount is adjusted, cavity air pressure is maintained 0.3Pa, intermediate frequency silicon target sputtering electricity is opened Source and pulsed bias power supply, regulation sputtering current are 7 A, and pulsed bias is -200 V, and dutycycle is 40%, treats transition region thickness Reach and closed after 200 nm.
C. MoS is deposited2/a-C:H multilayer films：Pulsed bias is controlled in -200 V, and dutycycle is 20%, the h of sedimentation time 2. Interval opens MoS2, graphite target, and alternately be passed through Ar, Ar/CH4Mixed gas alternating deposit MoS2Layer and a-C:H layers.Ar flows It is set as 65sccm, prepares individual layer MoS2During layer, MoS is opened2Shielding power supply, regulation sputtering current is 0.4 A, and is passed through Ar, is sunk The product time is 5 min；Prepare a-C:At H layers, MoS is closed2Shielding power supply, opens graphite shielding power supply, and regulation sputtering current is 14 A, Ar and N2Flow be respectively 65 sccm and 45 sccm, sedimentation time is 5 min.Modulation week is prepared in this approach Phase is 98 nm MoS2/a-C:H multilayer films.Plated film is cooled to temperature less than 40 DEG C after finishing, release vacuum takes out substrate.
Embodiment 2：
A. sample pretreatment：Smooth, clean titanium alloy planar substrates are placed in the true of non-balance magnetically controlled sputter coating machine After in cavity body, air pressure in vacuum chamber is evacuated to 6 × 10-3Below Pa, it is 0.5 Pa to be passed through high pure nitrogen to air pressure.Open arteries and veins Grid bias power supply is rushed, regulation voltage level is -1200V, carries out the min of argon plasma Bombardment and cleaning 20.
B. silicon transition zone is deposited：Argon flow amount is adjusted, cavity air pressure is maintained 1.0 Pa, mid frequency sputtering power supply is opened And pulsed bias power supply, regulation sputtering current is 3 A, and pulsed bias is -100 V, is closed after transition region thickness reaches 50 nm Close.
C. MoS is deposited2/a-C:H multilayer films：Pulsed bias is controlled in -400 V, and dutycycle is 50%, the h of sedimentation time 2. Interval opens MoS2, graphite target, and alternately be passed through Ar, Ar/CH4Mixed gas alternating deposit MoS2Layer and a-C:H layers.Ar flows It is set as 55sccm, prepares individual layer MoS2During layer, MoS is opened2Shielding power supply, regulation sputtering current is 0.1 A, and is passed through Ar, is sunk The product time is 15 min；Prepare a-C:At H layers, MoS is closed2Shielding power supply, opens graphite shielding power supply, and regulation sputtering current is 8 A, Ar and N2Flow be respectively 55 sccm and 55 sccm, sedimentation time is 15 min.Modulation week is prepared in this approach Phase is 334 nm MoS2/a-C:H multilayer films.Plated film is cooled to temperature less than 40 DEG C after finishing, release vacuum takes out substrate.
Embodiment 3：
A. sample pretreatment：Smooth, clean steel ball substrate is placed in the vacuum cavity of non-balance magnetically controlled sputter coating machine After interior, air pressure in vacuum chamber is evacuated to 6 × 10-3Below Pa, it is 1.0 Pa to be passed through high-purity argon gas to air pressure.Open pulsed bias Power supply, regulation voltage level is -600 V, carries out the min of argon plasma Bombardment and cleaning 30.
B. silicon transition zone is deposited：Argon flow amount is adjusted, cavity air pressure is maintained 0.5 Pa, mid frequency sputtering power supply is opened And pulsed bias power supply, regulation sputtering current is 8 A, and pulsed bias is -400 V, is closed after transition region thickness reaches 300 nm Close.
C. MoS is deposited2/a-C:H multilayer films：Pulsed bias is controlled in -600 V, and dutycycle is 70%, the h of sedimentation time 2. Interval opens MoS2, graphite target, and alternately be passed through Ar, Ar/CH4Gaseous mixture alternating deposit MoS2Layer and a-C:H layers.Ar flows are set It is set to 75sccm, prepares individual layer MoS2During layer, MoS is opened2Shielding power supply, regulation sputtering current is 0.5 A, and is passed through Ar, is deposited Time is 30 min；Prepare a-C:At H layers, MoS is closed2Shielding power supply, opens graphite shielding power supply, and regulation sputtering current is 18 A, Ar and N2Flow be respectively 75 sccm and 35 sccm, sedimentation time is 30 min.Modulation period is prepared in this approach For 628 nm MoS2/a-C:H multilayer films.Plated film is cooled to temperature less than 40 DEG C after finishing, release vacuum takes out substrate.

Claims (5)

1. a kind of technology of preparing of the thin-film material with multi-environment adaptability, it is characterised in that the preparation process of thin-film material is Complete, concretely comprise the following steps in the vacuum chamber of a non-balance magnetically controlled sputter coating machine：
A, activation cleaning surface：In the vacuum chamber that smooth, clean metallic substrates are placed in non-balance magnetically controlled sputter coating machine After be evacuated to 10-3 Below Pa, is passed through argon gas as ionization of gas, substrate applies pulsed bias, glow discharge produces plasma Body, plasma-activated cleaning is carried out to substrate surface；
It is prepared by B, transition zone：After cleaning is finished, silicon transition zone is prepared first using the method for non-balance magnetically controlled sputter, from high-purity Silicon is as sputtering target material, using argon gas as sputter gas, matrix extra-pulse back bias voltage, is closed after deposition certain thickness；
C, the method preparation MoS using unbalanced reactive magnetron sputtering2/a-C:H multilayered film materials：Sputtering target material selects MoS2 Target and graphite target, wherein preparing every layer of MoS2Layer and a-C:Reactant gas source at H layers is respectively：Ar and Ar/CH4, by changing target Electric current and CH4Be passed through the time, realize MoS2/a-C:H sandwich constructions alternating and mechanical periodicity, open intermediate frequency power supply and pulse is inclined Voltage source, depositional coating, plated film is cooled to temperature less than 40 DEG C after finishing, release vacuum takes out obtained thin-film material.
2. technology of preparing as claimed in claim 1, it is characterised in that in step, metallic substrates be selected from stainless steel, steel or Titanium alloy.
3. technology of preparing as claimed in claim 1, it is characterised in that in step, plasma-activated process parameters range For：The Pa of air pressure 0.2~3.0, pulsed bias -100~-1200V.
4. technology of preparing as claimed in claim 1, it is characterised in that in stepb, transition zone preparation technology parameter scope For：Cavity 0.2~1.0Pa of air pressure, the A of sputtering current 1~12, pulsed bias -50~-1000V, transition region thickness 30~500 nm。
5. technology of preparing as claimed in claim 1, it is characterised in that in step C, process parameters range is：Cavity air pressure 0.2~2.0Pa, Ar/CH4Volumetric flow of gas compares 6：1~1：6, pulsed bias -100~-1000V, the A of sputtering current 1~25, Modulation period is 5~1000 nm.
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GB201507524D0 (en) * 2015-05-01 2015-06-17 Teer Coatings Ltd Improvements to molybdenum containing coatings
CN107219030B (en) * 2016-03-21 2020-07-21 中国科学院深圳先进技术研究院 Film stress tester and testing method thereof
CN106868504B (en) * 2017-01-04 2019-02-19 兰州空间技术物理研究所 A kind of diesel engine piece surface multi-layer wear-resistant antifriction film and preparation method thereof
CN109576658B (en) * 2018-12-14 2020-03-27 西南交通大学 Preparation of dendritic amorphous MoS based on magnetron sputtering method2Method of nano-structuring
CN111490113A (en) * 2019-01-25 2020-08-04 清华大学 Photoelectric detection device and photoelectric conversion method
CN115551801A (en) * 2020-03-10 2022-12-30 新加坡国立大学 Seed layer, heterostructure including the seed layer, and method of forming material layer using the seed layer
CN111304616A (en) * 2020-04-03 2020-06-19 中国科学院兰州化学物理研究所 Preparation method of Ti and C doped molybdenum disulfide based nano composite film
CN111485212B (en) * 2020-06-04 2022-02-22 兰州文理学院 Preparation method of molybdenum disulfide-carbon multilayer film with sub-10-nanometer bionic structure
CN114107906B (en) * 2021-11-18 2022-07-15 中国地质大学（北京） Low-friction film for inner wall of solar panel driving bearing and preparation method thereof

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CN101550535B (en) * 2009-05-07 2010-09-29 上海交通大学 Method for preparing compound metal sulfide diamond composite membrane

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