CN102965618A - Preparation method of metal doped hydrogen-free diamond-like carbon film - Google Patents
Preparation method of metal doped hydrogen-free diamond-like carbon film Download PDFInfo
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- CN102965618A CN102965618A CN 201210519829 CN201210519829A CN102965618A CN 102965618 A CN102965618 A CN 102965618A CN 201210519829 CN201210519829 CN 201210519829 CN 201210519829 A CN201210519829 A CN 201210519829A CN 102965618 A CN102965618 A CN 102965618A
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Abstract
The invention discloses a preparation method of a metal doped hydrogen-free diamond-like carbon film which. The method is characterized in that an ion beam assisted deposition technology is utilized to prepare a metal doped hydrogen-free diamond-like film on a workpiece and a metal target and a graphite target are used for carrying out double-target sputtering. The preparation method comprises the following specific steps of: cleaning and activating ions on the surface of the workpiece and depositing to prepare the metal doped hydrogen-free diamond-like film. The prepared metal doped hydrogen-free diamond-like film has relatively higher film hardness, film-matrix binding force, elastic modulus, abrasion resistance, thermal stability and other performances. The preparation method is strong in technological operability and good in repeatability and can be applied to the surface treatment of silicon and various metal workpieces.
Description
Technical field
The present invention relates to the surface treatment of material, specifically a kind of deposition preparation of metal-doped non-hydrogen diamond membrane.
Background technology
Diamond like carbon film (DLC) is owing to its high hardness, low thermal expansivity and the low good characteristics such as frictional coefficient enjoy favor.But high internal stress, relatively relatively poor film-substrate cohesion and thermostability etc. have seriously limited extensively quoting of DLC.Diamond like carbon film at material surface deposition low-friction coefficient, high bond strength is the purpose that the plated film field will reach always, but this process is subject to the internal stress puzzlement always, higher internal stress very easily causes film in use to peel off from matrix, even in preparation process, peel off from substrate surface, limited the application of film.
Metal-doped diamond like carbon film can improve the toughness of film simultaneously greatly owing to have the internal stress lower than diamond like carbon film.Generally generally form metallic carbide owing to Performance of Mental Doped Diamond-like Carbon Film, so the hardness of diamond like carbon film also remains on higher scope.As mix W elements meeting and carbon formation W-C key in the tungsten diamond-like carbon film, and can improve the bonding force of film, improve the performances such as thermostability of film.
Metal-doped non-hydrogen diamond membrane is owing to have the internal stress lower than diamond like carbon film, better thermostability and better film-substrate cohesion, also kept simultaneously the feature performance benefit of diamond like carbon film high rigidity, low-friction coefficient, be applicable to the precision workpiece resistant surfaces and process.The metal refining doping contains hydrogen diamond membrane and relatively easily realizes, but it is lower to contain the hardness ratio of hydrogen diamond membrane own, and internal stress is relative also lower, and abrasion resistance properties is also relatively relatively poor under atmospheric condition.Simultaneously, there are the problems such as fine and close not, that surface quality is poor in the prepared film of traditional preparation means.Therefore the present invention adopts ion beam assisted deposition to prepare metal-doped diamond like carbon film, and film hardness is low when having overcome prior art and preparing film, and film-substrate cohesion is poor, the shortcomings such as surfaceness height.Prepared diamond like carbon film surface compact degree is high, and roughness is low, and film quality is better; The depositing temperature of film is low, has avoided causing the graphited problem of diamond like carbon film owing to excess Temperature in deposition process, has good process controllability.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect that existing diamond like carbon film technology exists, a kind of preparation method of metal-doped non-hydrogen diamond membrane is provided.It utilizes ion beam assisted deposition, use high purity metal target and graphite target, the metal-doped non-hydrogen diamond membrane of sputtering target material deposition preparation under the auxiliary bombardment effect of second source, the high rigidity of diamond like carbon film and the characteristics of low-friction coefficient have not only been kept, abrasion resistance properties and thermostability have greatly been improved again, reduced the internal stress of film, solved that the diamond like carbon film internal stress is high, film-substrate cohesion is poor and the problem of poor heat stability, can be widely used in the surface treatment of silicon and various metallic substance.
Realize that technical scheme of the present invention is: a kind of deposition preparation of metal-doped non-hydrogen diamond membrane is characterized in that comprising the following steps:
A. after workpiece being utilized the clean oven dry of deionized water ultrasonic cleaning, be fixed on the Work piece rotary disc in the ion beam assisted depositing filming equipment vacuum chamber, and vacuum chamber is vacuumized;
B. argon gas is passed into vacuum chamber, and keep the stable of vacuum tightness, open Work piece rotary disc, open ion source and second source respectively with workpiece and target material surface cleaning and activation;
C. source of the gas continues air feed, keeps vacustat, opens ion source and second source and mixes the tungsten non-hydrogen diamond membrane in the preparation of workpiece surface deposition;
D. close Work piece rotary disc, wait for that operating temperature fully reduces rear taking-up workpiece.
The vacuum tightness of described vacuum chamber is better than 2 * 10
-4Pa;
Described vacuum chamber passes in the argon gas process continuing, and vacustat is 1.2 * 10
-2～1.5 * 10
-2Pa;
Described ion source operating voltage is 2.0～3.5KV, and ion beam current is 20～100mA, and the working hour is 60min～180min;
To be purity carry out dual-target sputtering greater than 99.97% high purity metal target and high purity graphite target to described target;
Described metallic target material is any in tungsten (W), molybdenum (Mo), chromium (Cr), titanium (Ti), silver (Ag), copper (Cu), the zirconium (Zr);
Film preparation is carried out in the auxiliary bombardment of second source in the described ion source sputter deposition process, and second source voltage is 200V～800V, and beam current density is 20～100mA;
Described operating temperature is reduced to and is not higher than 50 ℃ and can takes out workpiece.
Metal-doped diamond like carbon film of the present invention has higher film hardness, film-substrate cohesion, Young's modulus, abrasion resistance and thermal stability.Technique is workable, and good reproducibility is applicable to the wear-resistant processing of silicon and all kinds of surface of workpieces.
Embodiment:
In order to understand better the present invention, describe by following specific embodiment.
Embodiment 1:
1, the stainless steel substrates ultrasonic cleaning is clean, after the oven dry, be fixed on the work rest in the ion beam assisted depositing filming equipment vacuum chamber and vacuumize forvacuum to 2.0 * 10
-4Pa;
2, connect plasma sputter source and second source source of the gas, argon gas is passed into vacuum chamber, keep air pressure to be lower than 1.3 * 10
-2Pa adopts voltage 2.7KV, and the ion beam current of electric current 100mA bombards target; Adopt voltage 0.2KV line 100mA that sample is carried out Bombardment and cleaning, bombardment time is 10min;
3, sputtering source voltage 2.7KV, the ion beam current bombardment graphite target of ion beam current 100mA; Voltage 2.7KV, the ion beam current bombardment tungsten target of line 25mA, second source adopts voltage 0.2KV, and line 20mA deposits non-hydrogen diamond membrane at workpiece surface, and depositing time is 120min;
4, deposition finishes, and closes the ion beam assisted depositing filming equipment, and keeps vacuum to treat the sample cooling, takes out sample when the sample table temperature is lower than 50 ℃, obtains W-DLC thin film at stainless steel substrates;
Prepared thicknesses of layers is about 1000nm, and W content is 3.08%, and internal stress is 0.24GP, film-substrate cohesion is 51N, surfacing (surfaceness is less than 30nm), nano hardness are 15.2GPa, and the average friction coefficient that with the GCr15 steel couple is rubbed under atmospheric environment is 0.26.Prepared film wear rate is 4.75 * 10
-6Mm
3/ Nm.
Embodiment 2:
1, the monocrystalline silicon piece ultrasonic cleaning is clean, after the oven dry, be fixed on the work rest in the ion beam assisted depositing filming equipment vacuum chamber and vacuumize forvacuum to 2.0 * 10
-4Pa;
2, connect plasma sputter source and second source source of the gas, argon gas is passed into vacuum chamber, keep air pressure to be lower than 1.5 * 10
-2Pa adopts voltage 2.7KV, and the ion beam current of electric current 100mA bombards target; Adopt voltage 0.2KV line 100mA that sample is bombarded; Bombardment time is 10min.
3, sputtering source voltage 2.7KV, the ion beam current bombardment graphite target of ion beam current 100mA; Voltage 2.5KV, the ion beam current bombardment chromium target of line 20mA, second source adopts voltage 0.25KV, and line 25mA deposits non-hydrogen diamond membrane at workpiece surface, and depositing time is 150min;
4, deposition finishes, and closes the ion beam assisted depositing filming equipment, and keeps vacuum to treat the sample cooling, takes out sample when the sample table temperature is lower than 50 ℃, obtains mixing the chromium diamond like carbon film at silicon chip.
Prepared thicknesses of layers is 1100nm, and chromium content is 5.37%, and internal stress is 0.23GP, film-substrate cohesion is 64N, surfacing (surface undulation is less than 30nm), nano hardness are 17.5GPa, and the average friction coefficient that with the GCr15 steel couple is rubbed under atmospheric environment is 0.23.Prepared film wear rate is 3.92 * 10
-6Mm
3/ Nm.
Claims (8)
1. a metal-doped non-hydrogen diamond membrane preparation method is characterized in that comprising the following steps:
A, workpiece utilized the clean oven dry of deionized water ultrasonic cleaning after, be fixed on the Work piece rotary disc in the ion beam assisted depositing filming equipment vacuum chamber, and vacuum chamber vacuumized;
B, argon gas is passed into vacuum chamber, and keep the stable of vacuum tightness, open Work piece rotary disc, open ion source and second source respectively with workpiece and target material surface cleans and activation;
C, source of the gas continue air feed, keep vacustat, open ion source and second source at the metal-doped non-hydrogen diamond membrane of workpiece surface deposition preparation;
D, close Work piece rotary disc, wait for that operating temperature fully reduces rear taking-up workpiece.
2. the preparation method of metal-doped non-hydrogen diamond membrane according to claim 1 is characterized in that the vacuum tightness of described vacuum chamber is better than 2 * 10
-4Pa.
3. according to the preparation method of right 1 described metal-doped non-hydrogen diamond membrane, it is characterized in that described vacuum chamber passes in the argon gas process continuing, vacustat is 1.2 * 10
-2～1.5 * 10
-2Between the Pa.
4. according to the preparation method of right 1 described metal-doped non-hydrogen diamond membrane, its described ion source operating voltage is 2.0～3.5KV according to different demand setting ranges, ion beam current 20～100mA, and the working hour is 60min～180min.
5. according to the preparation method of right 1 described metal-doped non-hydrogen diamond membrane, it is characterized in that described target is purity greater than 99.97% high purity metal target and graphite target, simultaneously sputters of two targets in the sputter deposition process.
6. according to the preparation method of right 1 described metal-doped non-hydrogen diamond membrane, it is characterized in that described metallic target material is any in tungsten (W), molybdenum (Mo), chromium (Cr), titanium (Ti), silver (Ag), copper (Cu), the zirconium (Zr).
7. according to the preparation method of right 1 described metal-doped non-hydrogen diamond membrane, it is characterized in that film preparation is carried out in the auxiliary bombardment of second source in the ion source sputter deposition process, be 0.2～0.8KV according to different demand second source voltage-regulation scopes, beam current density is 20～100mA.
8. according to the preparation method of right 1 described metal-doped non-hydrogen diamond membrane, its described operating temperature is reduced to and is not higher than 50 ℃ and can takes out workpiece.
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| CN106756847A (en) * | 2016-12-21 | 2017-05-31 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of witch culture DLC film |
| CN107338414A (en) * | 2016-05-03 | 2017-11-10 | 大连金泰表面工程科技有限公司 | Conduction, anticorrosive, wear-resistant, the preparation method of high-hardness diamond-like coating |
| CN108330443A (en) * | 2018-02-02 | 2018-07-27 | 北京鼎臣世纪超导科技有限公司 | A kind of diamond-like carbon film-coating method |
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| CN108385066A (en) * | 2018-02-26 | 2018-08-10 | 温州职业技术学院 | A kind of hydrogen-free metal doped diamond coating production and its product |
| CN109355624A (en) * | 2018-11-28 | 2019-02-19 | 福建工程学院 | A kind of tool surface diamond-like composite membrane |
| CN109423613A (en) * | 2017-08-31 | 2019-03-05 | 南京理工大学 | The preparation method of corrosion-resistant decorating film zirconium nitride |
| CN109423605A (en) * | 2017-08-31 | 2019-03-05 | 南京理工大学 | Titanium doped non-hydrogen diamond membrane, preparation method and applications |
| CN110241386A (en) * | 2018-03-09 | 2019-09-17 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and its preparation method and application |
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| CN107338414A (en) * | 2016-05-03 | 2017-11-10 | 大连金泰表面工程科技有限公司 | Conduction, anticorrosive, wear-resistant, the preparation method of high-hardness diamond-like coating |
| CN106175996A (en) * | 2016-06-30 | 2016-12-07 | 天津医科大学 | Surface has Invasive lumbar fusion device and the preparation method that rich silver nanoparticle multilayer film is modified |
| CN106756847A (en) * | 2016-12-21 | 2017-05-31 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of witch culture DLC film |
| CN106756847B (en) * | 2016-12-21 | 2019-03-22 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of witch culture DLC film |
| CN109423613A (en) * | 2017-08-31 | 2019-03-05 | 南京理工大学 | The preparation method of corrosion-resistant decorating film zirconium nitride |
| CN109423605A (en) * | 2017-08-31 | 2019-03-05 | 南京理工大学 | Titanium doped non-hydrogen diamond membrane, preparation method and applications |
| CN108330443A (en) * | 2018-02-02 | 2018-07-27 | 北京鼎臣世纪超导科技有限公司 | A kind of diamond-like carbon film-coating method |
| CN108385066A (en) * | 2018-02-26 | 2018-08-10 | 温州职业技术学院 | A kind of hydrogen-free metal doped diamond coating production and its product |
| CN110241386A (en) * | 2018-03-09 | 2019-09-17 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and its preparation method and application |
| CN110241386B (en) * | 2018-03-09 | 2024-02-09 | 深圳先进技术研究院 | Boron-doped diamond electrode and preparation method and application thereof |
| CN108342677A (en) * | 2018-03-13 | 2018-07-31 | 中国神华能源股份有限公司 | The wheel and its manufacturing method of rolling stock |
| CN109355624A (en) * | 2018-11-28 | 2019-02-19 | 福建工程学院 | A kind of tool surface diamond-like composite membrane |
| CN110527964A (en) * | 2019-09-03 | 2019-12-03 | 上海大学 | A kind of diamond-like carbon composite film and its preparation method and application and a kind of IGBT module heat-radiating substrate |
| CN110527964B (en) * | 2019-09-03 | 2020-07-31 | 上海大学 | Diamond-like composite film, preparation method and application thereof, and IGBT module radiating substrate |
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Application publication date: 20130313 |