CN102586735B - Hydrogen-free silicon incorporated diamond film and preparation method thereof - Google Patents
Hydrogen-free silicon incorporated diamond film and preparation method thereof Download PDFInfo
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- CN102586735B CN102586735B CN201210072931.3A CN201210072931A CN102586735B CN 102586735 B CN102586735 B CN 102586735B CN 201210072931 A CN201210072931 A CN 201210072931A CN 102586735 B CN102586735 B CN 102586735B
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 41
- 239000010432 diamond Substances 0.000 title claims abstract description 41
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000010703 silicon Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011159 matrix material Substances 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- -1 argon ions Chemical class 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
A hydrogen-free silicon incorporated diamond film is characterized by being sequentially composed of a base body (1), a metal layer (2), a metal carbide layer (3) and a silicon incorporated diamond film (4). A preparation method comprises the steps of adopting a direct current magnetron sputtering graphite target, an intermediate frequency magnetron sputtering silicon carbide target or a silicon target and an ion source to assist deposition, and sequentially cleaning the base body through argon ions; depositing the metal layer and the metal carbide layer; and depositing the hydrogen-free silicon incorporated diamond film. Compared with the prior art, the film prepared by the preparation method has the advantages of being low in friction coefficient and abrasion rate and good in quality. The film preparation process is simple, repeatability is good, hydrogen-free silicon incorporated diamond films with different silicon contents can be prepared, the precision requirement of precise instrument transmission parts can be met under the specific environments including humidity changes and the like, the precision, the sensitivity and the reliability of the hydrogen-free silicon incorporated diamond film in use are improved, and the hydrogen-free silicon incorporated diamond film is suitable for ultra-integrated circuits, medical instruments, optical components, radars, aircrafts and the like.
Description
Technical field
The present invention relates to a kind of metallic surface rete and preparation method thereof, particularly a kind of without hydrogen Si blended imitation diamond rete and preparation method thereof.
Background technology
Diamond-like carbon film (Diamond-like carbon, DLC) has high rigidity, compared with low frictional coefficient and good wear resistance and obtain a wide range of applications.But the internal stress that two subject matters of restriction DLC rete application are retes is larger, causes the combination degree between rete and matrix poor; In addition, DLC rete is very responsive to the variation of ambient moisture, there are some researches show, the frictional coefficient of DLC rete increases along with the increase of ambient moisture, is difficult to the frictional coefficient that keeps lower under high humidity.Fast development along with modern science and technology, requirement aspect tolerance range to precision drive parts under varying environment, reliability, sensitivity and transmission efficiency is more and more higher, therefore, the doped diamond-like film layer with excellent mechanical performances and wear resisting property of development of new is extremely urgent.In recent years, researcher further improved the over-all properties of quasi-diamond rete by add metal or non-metallic element in rete.Wherein, in quasi-diamond rete, mix internal stress, the raising thermal stability that Si element not only can reduce rete, but also can reduce the susceptibility that rete changes ambient moisture.It is reported, Si content is 3～6% time, and the frictional coefficient of quasi-diamond rete is subject to the variation of ambient moisture very little, can greatly improve the precision of precision instrument.
At present, prepared Si-DLC rete is mainly divided into hydrogeneous Si blended imitation diamond rete (Si-DLC (H)) and without two kinds of hydrogen Si blended imitation diamond retes (Si-DLC).At present, what great majority research was reported is the preparation of hydrogeneous Si blended imitation diamond rete, and the composite deposition technology of mainly using radio frequency plasma chemical vapour deposition technique, chemical vapour deposition and physical vapor deposition to combine, has advantages of that sedimentation rate is fast.But, these some shortcomings of preparation method's ubiquity: the hardness of (1) rete own is relatively low, and the abrasion resistance properties under atmospheric condition is relatively poor; (2) adopt radio frequency plasma chemical vapour deposition technique, conventionally use the hydrocarbon gas containing Si, as SiH
4or Si (CH
3)
4as Si source.The introducing of hydrogen not only can destroy the three-dimensional net structure of Si blended imitation diamond rete, and then reduces its mechanical property, and great majority are poisonous containing the hydrocarbon gas of Si, and the health of human body and environment are had to very large harm; (3) there is certain harm hidden danger to equipment and operator in radio-frequency power supply.
At present, less without the preparation research report of hydrogen Si blended imitation diamond rete.CN101109064A discloses a kind of plating method of silicon doped non-hydrogen diamond membrane.Zhao Dong just waits people (Acta Physica Sinica, 2008,57 (3)) to utilize pulse arc ion plate technology, and the quantity of mixing 3 SiC 2/graphite target and pure graphite target by adjustment is prepared the quasi-diamond rete of different silicon-containing amount.Research shows, the frictional coefficient of the Si-DLC rete of the different silicon-containing amount that this technology is prepared changes greatly, and when silicon content is less than 6.17at.%, frictional coefficient is 0.15; When silicon content is during up to 28at.%, the frictional coefficient of rete rises to 0.7 very soon.(Surface and Coatings Technology 163～164,2003 144-148) adopts double source filtering cathode arc ion plating (aip) deposition Si-DLC rete to the people such as Monteiro.Research shows, prepared silicon content 3at.%, 5at.%, the Si-DLC rete of 6at.%, and when loaded load is 0.2～0.4N, frictional coefficient is all more than 0.20.More than report all adopts arc ion plating (aip) to prepare Si blended imitation diamond film, and the frictional coefficient of rete is relatively high, is difficult to meet the application requiring of precision drive parts.
Summary of the invention
The present invention is directed at present without the higher problem of hydrogen Si blended imitation diamond rete frictional coefficient, provide that a kind of film/film-substrate binding strength is high, sedimentation rate is very fast, frictional coefficient and wear rate lower without hydrogen Si blended imitation diamond rete.
Another object of the present invention is to provide a kind of above-mentioned preparation method without hydrogen Si blended imitation diamond rete.
The present invention is achieved by the following technical solutions: described without hydrogen Si blended imitation diamond rete successively by matrix 1; Metal level 2; Metal carbide layer 3; Si blended imitation diamond rete 4 forms.
Described matrix is die steel, stainless steel or Wimet.
Preparation method without hydrogen Si blended imitation diamond rete of the present invention adopts magnetically controlled DC sputtering graphite target, medium frequency magnetron sputtering carbonization silicon target or silicon target and ion source assistant depositing, and base vacuum degree is less than 5 * 10
-3pa, 150～250 ℃ of temperature, under work rest rotating speed 1～5rpm condition, in turn include the following steps:
(1) argon ion cleans matrix: argon flow amount 120～300sccm, furnace pressure 0.20～0.6Pa, ion source power 400～600W, bias voltage 600～1000V, scavenging period 10～30min;
(2) depositing metal layers and metal carbide layer: argon flow amount 120～240sccm, furnace pressure 0.2～0.4Pa, ion source power 200～500W; During depositing metal layers, metallic target sputtering power 800～1000W, bias voltage 400～600V, depositing time 10～20min; During deposited metal carbide layer, metallic target sputtering power 600～1000W; Graphite target sputtering power 1200～2000W, bias voltage 100～200V, depositing time 10～30min;
(3) deposit without hydrogen Si blended imitation diamond rete: argon flow amount 100～200sccm, bias voltage 50～150V, furnace pressure 0.2～0.4Pa.SiC target or Si target sputtering power 50～650W, graphite target sputtering power 1600～2000W, ion source power 100～400W, depositing time 4～6h.
Described metallic target is Cr, Ti or W target.
It is a kind of without hydrogen Si blended imitation diamond rete and preparation method thereof that patent of the present invention provides, first use magnetron sputtering technique depositing metal layers and metal carbide layer, then adopt magnetically controlled DC sputtering graphite target to prepare quasi-diamond rete, simultaneously with medium frequency magnetron sputtering SiC target or the Si target Si element that adulterates, during the work of intermediate frequency target, replace as negative electrode or anode, the phenomenon that can effectively suppress target surface " sparking " and " disappearing anode ", can improve again the sedimentation rate of rete; In whole coating process, adopt ion source assistant depositing, further improve ionization level, thereby can improve the performances such as hardness, wear resistance and bonding force of rete.Adopt the compound deposition method of these many technology, can prepare excellent combination property without hydrogen Si blended imitation diamond film.
Accompanying drawing explanation
Fig. 1 is matrix/Me/MeC/Si-DLC rete schematic diagram.Wherein 1 is matrix; 2 is metal level; 3 is metal carbide layer; 4 is without hydrogen Si blended imitation diamond rete.
Embodiment
The present invention can further illustrate by following examples.Adopt magnetically controlled DC sputtering graphite target, medium frequency magnetron sputtering carbonization silicon target or silicon target and ion source assistant depositing without hydrogen, to mix the quasi-diamond rete of silicon.Gas is the argon gas of purity 99.99%.
Matrix is die steel, by the listed technical process of table 1 and parameter, operates successively.Prepared Si-DLC thicknesses of layers is 1.08 μ m, and silicon content is 3.61at.%, and the bonding strength between rete and matrix is 62N, and nano hardness is 11.23GPa; The frictional coefficient of Si-DLC rete under relative humidity 40% and 70% environment is respectively 0.139 and 0.150, and wear rate is 3.38 * 10
-10mm
3n
-1m
-1.
Table 1 embodiment 1 technical process table
Matrix is stainless steel, by the listed technical process of table 2 and parameter, operates successively.Prepared Si-DLC thicknesses of layers is 1.8 μ m, and silicon content is 15.2at.%, and the bonding strength between rete and matrix is 57N, and nano hardness is 16.3GPa; The frictional coefficient of Si-DLC rete under relative humidity 40% and 70% environment is respectively 0.127 and 0.160, and wear rate is 4.9 * 10
-10mm
3n
-1m
-1.
Table 2 embodiment 2 technical process tables
Matrix is Wimet, by the listed technical process of table 3 and parameter, operates successively.Prepared Si-DLC thicknesses of layers is 2.6 μ m, and silicon content is 28.63at.%, and the bonding strength between rete and matrix is 55N, and nano hardness is 9.9GPa; The frictional coefficient of Si-DLC rete under relative humidity 40% and 70% environment is respectively 0.095 and 0.146, and wear rate is 1.45 * 10
-9mm
3n
-1m
-1.
Table 3 embodiment 3 technical process tables
The main performance index without hydrogen Si blended imitation diamond rete of preparing by the present invention is in Table 4.
Table 4 is without main performance index and the testing standard of hydrogen Si blended imitation diamond rete
Illustrate: the test condition of the frictional coefficient of this rete: MS-T3000 ball dish friction and wear tester, mating material is the GCr15 steel ball of diameter of phi 4mm, line of slide speed 0.2m/s, load 0.49～9.8N; 23～25 ℃ of the temperature of test, the ambient relative humidity 40～70% of test.
Table 4 test result shows, compares the feature that the prepared rete of the inventive method has frictional coefficient and wear rate is low, film quality is good with existing arc ions electroplating method preparation without hydrogen Si blended imitation diamond rete.Film preparation technique of the present invention is simple, reproducible, can prepare different silicon-containing amount without hydrogen Si blended imitation diamond rete, can meet the requirement of precision instrument drive disk assembly precision under the specific environments such as humidity variation, the precision, sensitivity and the reliability that improve its use, be applicable to super unicircuit, medical equipment, optical element, radar, aviation aircraft etc.
Claims (2)
1. without a hydrogen Si blended imitation diamond rete, it is characterized in that described without hydrogen Si blended imitation diamond rete successively by matrix (1); Metal level (2); Metal carbide layer (3); Si blended imitation diamond rete (4) forms; Its preparation method is to adopt magnetically controlled DC sputtering graphite target, medium frequency magnetron sputtering carbonization silicon target or silicon target and ion source assistant depositing, and base vacuum degree is less than 5 * 10
-3pa, 150 ~ 250 ℃ of temperature, under work rest rotating speed 1 ~ 5rpm condition, are comprised of following steps successively:
(1) argon ion cleans matrix: argon flow amount 120 ~ 300sccm, furnace pressure 0.20 ~ 0.6Pa, ion source power 400 ~ 600W, bias voltage 600 ~ 1000V, scavenging period 10 ~ 30min;
(2) depositing metal layers and metal carbide layer: argon flow amount 120 ~ 240sccm, furnace pressure 0.2 ~ 0.4Pa, ion source power 200 ~ 500W; During depositing metal layers, metallic target sputtering power 800 ~ 1000W, bias voltage 400 ~ 600V, depositing time 10 ~ 20min; During deposited metal carbide layer, metallic target sputtering power 600 ~ 1000W; Graphite target sputtering power 1200 ~ 2000W, bias voltage 100 ~ 200V, depositing time 10 ~ 30min;
(3) deposit without hydrogen Si blended imitation diamond rete: argon flow amount 100 ~ 200sccm, bias voltage 50 ~ 150V, furnace pressure 0.2 ~ 0.4Pa, SiC target or Si target sputtering power 50 ~ 650W, graphite target sputtering power 1600 ~ 2000W, ion source power 100 ~ 400W, depositing time 4 ~ 6h.
2. according to claim 1 without hydrogen Si blended imitation diamond rete, it is characterized in that described metallic target is Cr, Ti or W target.
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| CN105734527B (en) * | 2016-03-08 | 2019-01-18 | 仪征亚新科双环活塞环有限公司 | A kind of diamond-like coating, piston ring and preparation process for piston ring surface |
| CN107267941A (en) * | 2017-06-13 | 2017-10-20 | 广东省新材料研究所 | A kind of hydrogeneous preparation method for mixing aluminium DLC film |
| CN107557752A (en) * | 2017-09-05 | 2018-01-09 | 贝原合金（苏州）有限公司 | Multilayer diamond-like film and its processing method |
| CN109182997B (en) * | 2018-09-19 | 2020-06-16 | 西安交通大学 | Preparation method of Si-doped diamond-like coating |
| CN109609919A (en) * | 2018-12-27 | 2019-04-12 | 广东省新材料研究所 | A kind of composite diamond film and preparation method thereof |
| CN112707367B (en) * | 2020-12-30 | 2024-02-27 | 中国人民解放军陆军工程大学 | Diamond-like protective film and preparation method thereof |
| CN115233224B (en) * | 2022-06-30 | 2023-12-05 | 湖南碳康生物科技有限公司 | TC4 material with wear-resistant surface and low biotoxicity and preparation method thereof |
| CN114990510B (en) * | 2022-07-18 | 2022-10-28 | 湖南碳康生物科技有限公司 | Medical stainless steel material and preparation method thereof |
| CN116904925A (en) * | 2023-07-21 | 2023-10-20 | 广东省科学院新材料研究所 | High-temperature super-lubrication silicon-doped diamond-like carbon film and preparation method and application thereof |
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| CN100516286C (en) * | 2004-12-24 | 2009-07-22 | 鸿富锦精密工业（深圳）有限公司 | Method for hard coating thin film of generic diamond |
| CN101109064A (en) * | 2007-08-15 | 2008-01-23 | 中国航天科技集团公司第五研究院第五一○研究所 | Method of plating-manufacturing silicon doped non-hydrogen diamond membrane |
| CN101597745A (en) * | 2008-06-02 | 2009-12-09 | 中国航天科技集团公司第五研究院第五一○研究所 | A kind of deposition method of TiC/DLC multilayer film |
| CN101787518A (en) * | 2010-03-24 | 2010-07-28 | 中国地质大学（北京） | Multi-ion-beam sputter-deposition technology for doping with diamond-like carbon (DLC) coating |
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