CN102277556A - Method for preparing nano composite ultra-hard thin film - Google Patents
Method for preparing nano composite ultra-hard thin film Download PDFInfo
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- CN102277556A CN102277556A CN 201110237494 CN201110237494A CN102277556A CN 102277556 A CN102277556 A CN 102277556A CN 201110237494 CN201110237494 CN 201110237494 CN 201110237494 A CN201110237494 A CN 201110237494A CN 102277556 A CN102277556 A CN 102277556A
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Abstract
The invention belongs to the field of preparation of thin film materials and particularly relates to a method for preparing the nano composite ultra-hard thin film. The method comprises: firstly, depositing MeN on a substrate by means of magnetic filtered arc plasma deposition to form a 50-nanometer-thick MeN thin film serving as a transitional layer; secondly, continuing depositing MeN by means of magnetic filtered arc plasma deposition and co-depositing Si3N4 on the substrate by means of ion beam sputtering at the same time, wherein a direct current back bias voltage of -100V is applied onto the substrate in the process of co-deposition; and finally, obtaining the nanocrystalline MeN/amorphous Si3N4 nano composite ultra-hard thin film. In the invention, the magnetic filtered arc plasma deposition and the ion beam sputtering are combined and compensate each other for disadvantages on the basis of a characteristic that the working air pressure of the magnetic filtered arc plasma deposition is similar to that of the ion beam sputtering, and thus, the nanocrystalline MeN/amorphous Si3N4 nano composite ultra-hard thin film with high film and substrate bonding force is obtained.
Description
Technical field
The invention belongs to the thin-film material preparation field, be specifically related to a kind of preparation method of nano composite super-hard film.
Background technology
Abominable actual industrial and mineral condition such as some high temperature, impact, heavy duty, strong corrosive medium makes that the research and development of sufacing in recent years obtain significant progress, becomes the emerging field that scientific and technological circle attract people's attention.Hard thin film material enjoys material circle to pay close attention to as the effective means of improving the workpiece surface performance.Professor S.Veprek has proposed the design concept of nanocrystalline (nc)/amorphous (α) composite construction the earliest, and general formula is expressed as nc-MeN/ α-Si
3N
4
(Me=Ti,?Cr、Zr、V)。Its microstructure generally is that the crystalline phase of nc-MeN nano-scale evenly is embedded in α-Si
3N
4In the amorphous skeleton matrix (skeleton thickness＜1nm).The hardness of this nano compound film has surpassed 40GPa, becomes the new super-hard film material of a class.This type of superhard film has overcome the periodic structure error of preparation superlattice superhard films and the complicacy of technology, and this type of film demonstrates extremely superior mechanical property (particularly obdurability collaborative strengthen, up to the elastic restoration ratio 90% or more), good chemical stability (as the oxidation-resistance above 1000 ℃ and good erosion resistance) etc., has huge application advantage in the frictional wear field.
CVD and PVD method all are used for preparing nc-MeN/ α-Si
3N
4(Me=Ti, Cr, Zr, V) Development of Superhard Nanocomposite Films.CVD method shortcoming is depositing temperature too high (900 ~ 1200 ℃), has surpassed the conventional thermal treatment temp of steel tool and mould, and the silane gas of using simultaneously is explosive, poor stability.PVD film-forming temperature low (300 ~ 500 ℃), silicon is by the solid target as sputter, and is safe, but ionization level is low, and the reduction of depositing temperature reduces density of film, film substrate bond strength.Therefore, some novel PVD technology occur in succession, and wherein magnetic filtering cathode arc plasma deposition technique enjoys favor.It is worked in the arc discharge mode, has high ionization level, and the characteristics of high ion energy can be in room temperature or synthesis of densified under near the condition of room temperature, compound that film-substrate cohesion is high or alloy film.Preparation nc-MeN/ α-Si
3N
4Si content is vital factor in the nano composite super-hard film, the silicon source can be provided by cathode arc, because cathode arc requires target to have preferably electric conductivity and heat expansion ability, and the electric conductivity of silicon is relatively poor, even use high conductive silicon, cost height own, its relatively poor heat expansion ability also can cause the target cracking simultaneously.If adopt Me-Si alloy or composition target, this type of alloy or composition target are smelted, the processing technology complexity, and cost is higher, and the Me/Si ratio of target is certain simultaneously, and thin film composition is difficult to flexible control.The silicon source is necessary to introduce by other modes.
Summary of the invention
The purpose of this invention is to provide a kind of mode of magnetic filtering cathode arc and ion beam sputtering codeposition that adopts and prepare nanocrystalline M eN/ amorphous Si
3N
4The method of Development of Superhard Nanocomposite Films (Me=Ti, Cr, Zr, V).
The present invention is by the following technical solutions:
A kind of preparation method of Development of Superhard Nanocomposite Films is characterized in that, described Development of Superhard Nanocomposite Films is nanocrystalline M eN/ amorphous Si
3N
4Development of Superhard Nanocomposite Films, wherein Me is Ti, Cr, Zr, V, preparation process comprises: (1) is inserted substrate in the vacuum chamber, and vacuum is evacuated to 5.0 * 10
-4Pa; (2) adopt the basad upper deposition MeN of mode of magnetic filtered arc ion plating to form the MeN film of 50-100 nanometer thickness as transition zone; (3) continue to adopt the mode of magnetic filtered arc ion plating to deposit MeN, adopt simultaneously the basad upper codeposition Si of mode of ion beam sputtering
3N
4, in the codeposition process substrate is applied-the 100V dc negative bias voltage, thereby makes nanocrystalline M eN/ amorphous Si
3N
4Development of Superhard Nanocomposite Films.
When the mode of employing magnetic filtered arc ion plating deposited MeN, be specially: place, magnetic filtering cathode source fed N
2/ Ar gas mixture, wherein the Ar flow is 7.0sccm, N
2Flow is 21.0sccm, and the striking of anticathode Me target produces arc discharge, draws ionic fluid, thereby deposit MeN in substrate, and operating air pressure is 0.1 ~ 0.3Pa.
The cathodic current in described magnetic filtering cathode source is 55 ~ 70A, and the source coil current is 0.25-0.5A, and it is 1.0 ~ 4.0A that magnetic filters coil current, and the egress line loop current is 1.5A.
Adopt the mode of ion beam sputtering to deposit Si
3N
4The time, specifically adopt the Kaufman ion gun to carry out ion beam sputtering, the Ar flow of Kaufman ion gun is 8.0sccm, and plate voltage is 1500 ~ 1700V, and accelerating potential is 120V, and the cathodic discharge electric current is 10A, line is 50mA, Ar ion beam sputtering α-Si
3N
4Target, thereby deposition Si
3N
4, operating air pressure is 0.1 ~ 0.3Pa.
Described substrate is carried out pre-treatment earlier before inserting vacuum chamber, and preprocessing process is: substrate is put into acetone, ethanol ultrasonic cleaning successively after oil removing, polishing, takes out the back and dries up with nitrogen.
The material of described substrate is titanium alloy (TC4), bearing steel (GCr15), die steel (5CrMnMo).
The present invention combines the ion plating of magnetic filtered arc with ion beam sputtering, utilize the close characteristics of operating air pressure of the two, mutually covers the shortage, at preparation nanocrystalline M eN/ amorphous Si
3N
4During nano compound film, deposited with the good MeN film of substrate caking power as transition zone by the mode of magnetic filtered arc ion plating earlier; The mode of magnetic filtered arc ion plating deposits MeN then, and the mode of simultaneously ion beam sputtering deposits Si
3N
4, obtain the good nanocrystalline M eN/ of film-substrate cohesion amorphous Si
3N
4Nano compound film, 1 micron of film thickness, wherein MeN is embedded in Si with the nanometer crystalline phase
3N
4On the matrix, its nano hardness is between 40GPa-60GPa.
The ion plating of magnetic filtered arc can separate flexible modulation with the parameter of ion beam sputtering, and the ion plating of magnetic filtered arc can be regulated and control density, the energy of deposition ion, ion beam sputtering Si flexibly
3N
4Target provides the silicon source, has remedied the magnetic filtered arc and has plated the deficiency that should not use silicon target, and the two does not interfere with each other displays one's respective advantages, and can prepare the good super hard nano composite film of film-substrate cohesion, improves service life and the production efficiency of workpiece.Find that in preparation technology apply the substrate negative bias grain-size, the film hardness of silicone content, TiN played a decisive role, this nano composite structure that obtains is the ideal tissue that obtains excellent mechanical property under these processing condition.
Description of drawings
Fig. 1 is the nc-TiN/ α-Si of embodiment 1 preparation
3N
4The section transmission electron microscope image of nano composite super-hard membrane material.
Embodiment
Embodiment 1:
Nanocrystalline TiN/ amorphous Si
3N
4The preparation of nano compound film:
(1) with substrate after oil removing, polishing, put into acetone, ethanol ultrasonic cleaning successively, take out the back and dry up with nitrogen and inserts in the vacuum chamber, vacuum is evacuated to 5.0 * 10
-4Pa;
(2) feed N from the magnetic filtering cathode source
2/ Ar gas mixture, wherein the Ar flow is 7.0sccm, N
2Flow is 21.0sccm, anticathode high-purity Ti target (purity 99.96%) striking produces arc discharge, cathodic current 70A, the source coil current is 0.25A, magnetic filters coil current 3.0A, and egress line loop current 1.5A draws ionic fluid, the TiN film of deposition 50 nanometer thickness in substrate, operating air pressure is 0.2Pa;
(3) produce the Ar ion beam by the Kaufman ion gun then, the Ar flow is 8.0sccm, plate voltage 1600V, accelerating potential 120V, cathodic discharge electric current 10A, line 50mA, ion beam sputtering α-Si
3N
4Target (purity 99.99%) is with 2) described in the magnetic filtering cathode arc work simultaneously TiN and Si
3N
4Jointly be deposited on the nanocrystalline TiN/ amorphous Si of preparation in the substrate
3N
4Laminated film applies-the 100V dc negative bias voltage operating air pressure 0.1Pa to substrate in the codeposition process.
Under above-mentioned process conditions, obtained nanocrystalline TiN/ amorphous Si
3N
4Nano composite film, its section transmission electron microscope image as shown in Figure 1, detect by analysis, film thickness is 1 micron, TiN crystal grain is diameter 2 nanometers, and the columnar nanometer crystal grain of long 10 nanometers is in the nanocrystalline silicon nitride amorphous phase that evenly is embedded in about 1nm, intercrystalline amorphous phase thickness only is that the nano hardness of film is at 46GPa about 1 nanometer.
Embodiment 2:
Nanocrystalline CrN/ amorphous Si
3N
4The preparation of nano compound film:
(1) with substrate after oil removing, polishing, put into acetone, ethanol ultrasonic cleaning successively, take out the back and dry up with nitrogen and inserts in the vacuum chamber, vacuum is evacuated to 5.0 * 10
-4Pa;
(2) feed N from the magnetic filtering cathode source
2/ Ar gas mixture, wherein the Ar flow is 7.0sccm, N
2Flow is 21.0sccm, the high-purity Cr target of anticathode (purity 99.96%) striking produces arc discharge, cathodic current 65A, the source coil current is 0.5A, magnetic filters coil current 3.0A, and egress line loop current 1.5A draws ionic fluid, the CrN film of deposition 80 nanometer thickness in substrate, operating air pressure is 0.2Pa;
(3) produce the Ar ion beam by the Kaufman ion gun then, the Ar flow is 8.0sccm, plate voltage 1700V, accelerating potential 120V, cathodic discharge electric current 10A, line 50mA, ion beam sputtering α-Si
3N
4Target (purity 99.99%) is with 2) described in the magnetic filtering cathode arc work simultaneously CrN and Si
3N
4Jointly be deposited on the nanocrystalline CrN/ amorphous Si of preparation in the substrate
3N
4Laminated film applies-the 100V dc negative bias voltage operating air pressure 0.1Pa to substrate in the codeposition process.
Under above-mentioned process conditions, obtained nanocrystalline CrN/ amorphous Si
3N
4Nano composite film, the nano hardness of film is at 41GPa.
Embodiment 3:
Nanocrystalline ZrN/ amorphous Si
3N
4The preparation of nano compound film:
(1) with substrate after oil removing, polishing, put into acetone, ethanol ultrasonic cleaning successively, take out the back and dry up with nitrogen and inserts in the vacuum chamber, vacuum is evacuated to 5.0 * 10
-4Pa;
(2) feed N from the magnetic filtering cathode source
2/ Ar gas mixture, wherein the Ar flow is 7.0sccm, N
2Flow is 21.0sccm, the high-purity Zr target of anticathode (purity 99.96%) striking produces arc discharge, cathodic current 70A, the source coil current is 0.5A, magnetic filters coil current 3.0A, and egress line loop current 1.5A draws ionic fluid, the ZrN film of deposition 100 nanometer thickness in substrate, operating air pressure is 0.2Pa;
(3) produce the Ar ion beam by the Kaufman ion gun then, the Ar flow is 8.0sccm, plate voltage 1600V, accelerating potential 120V, cathodic discharge electric current 10A, line 50mA, ion beam sputtering α-Si
3N
4Target (purity 99.99%) is with 2) described in the magnetic filtering cathode arc work simultaneously ZrN and Si
3N
4Jointly be deposited on the nanocrystalline ZrN/ amorphous Si of preparation in the substrate
3N
4Laminated film applies-the 100V dc negative bias voltage operating air pressure 0.1Pa to substrate in the codeposition process.
Under above-mentioned process conditions, obtained nanocrystalline ZrN/ amorphous Si
3N
4Nano composite film, the nano hardness of film is at 43GPa.
Claims (5)
1. the preparation method of a Development of Superhard Nanocomposite Films is characterized in that, described Development of Superhard Nanocomposite Films is nanocrystalline M eN/ amorphous Si
3N
4Development of Superhard Nanocomposite Films, wherein Me is Ti, Cr, Zr, V, preparation process comprises: (1) is inserted substrate in the vacuum chamber, and vacuum is evacuated to 5.0 * 10
-4Pa; (2) adopt the basad upper deposition MeN of mode of magnetic filtered arc ion plating to form the MeN film of 50-100 nanometer thickness as transition zone; (3) continue to adopt the mode of magnetic filtered arc ion plating to deposit MeN, adopt simultaneously the basad upper codeposition Si of mode of ion beam sputtering
3N
4, in the codeposition process substrate is applied-the 100V dc negative bias voltage, thereby makes nanocrystalline M eN/ amorphous Si
3N
4Development of Superhard Nanocomposite Films.
2. the preparation method of nano composite super-hard film as claimed in claim 1 is characterized in that, when the mode of employing magnetic filtered arc ion plating deposited MeN, be specially: place, magnetic filtering cathode source fed N
2/ Ar gas mixture, wherein the Ar flow is 7.0sccm, N
2Flow is 21.0sccm, and the striking of anticathode Me target produces arc discharge, draws ionic fluid, thereby deposit MeN in substrate, and operating air pressure is 0.1 ~ 0.3Pa.
3. the preparation method of nano composite super-hard film as claimed in claim 2, it is characterized in that the cathodic current in described magnetic filtering cathode source is 55 ~ 70A, the source coil current is 0.25-0.5A, it is 1.0 ~ 4.0A that magnetic filters coil current, and the egress line loop current is 1.5A.
4. the preparation method of Development of Superhard Nanocomposite Films as claimed in claim 1 is characterized in that, adopts the mode of ion beam sputtering to deposit Si
3N
4The time, specifically adopt the Kaufman ion gun to carry out ion beam sputtering, the Ar flow of Kaufman ion gun is 8.0sccm, and plate voltage is 1500 ~ 1700V, and accelerating potential is 120V, and the cathodic discharge electric current is 10A, line is 50mA, Ar ion beam sputtering α-Si
3N
4Target, thereby deposition Si
3N
4, operating air pressure is 0.1 ~ 0.3Pa.
5. as the preparation method of each described nano composite super-hard film of claim 1-4, it is characterized in that described substrate is carried out pre-treatment earlier before inserting vacuum chamber, preprocessing process is: substrate is after oil removing, polishing, put into acetone, ethanol ultrasonic cleaning successively, take out the back and dry up with nitrogen.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106906442A (en) * | 2015-12-23 | 2017-06-30 | 中国科学院宁波材料技术与工程研究所 | A kind of coating with high rigidity and self lubricity and preparation method thereof |
| CN109423613A (en) * | 2017-08-31 | 2019-03-05 | 南京理工大学 | The preparation method of corrosion-resistant decorating film zirconium nitride |
| CN112626519A (en) * | 2020-12-16 | 2021-04-09 | 蚌埠飞宇轴承有限公司 | Processing technology for bearing element for prolonging fatigue life of rolling bearing |
| CN113463023A (en) * | 2021-04-29 | 2021-10-01 | 华东师范大学 | Preparation method of silicon nitride composite film for surface abrasion resistance of medical instrument die |
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| JP2004074361A (en) * | 2002-08-20 | 2004-03-11 | Sumitomo Electric Ind Ltd | Coated hard tool |
| CN1654702A (en) * | 2005-02-16 | 2005-08-17 | 吴大维 | High oxidation resistance nanocrystalline-amorphous structured superhard composite film cutting tool and deposition method therefor |
| CN1804113A (en) * | 2006-01-19 | 2006-07-19 | 上海交通大学 | Method for preparing Ti-Si-N film by adjusting gas partial pressure of magnetic controlled sputtering reaction |
| CN101457359A (en) * | 2008-11-14 | 2009-06-17 | 武汉大学 | Method for preparing Ti-Si-N nanocrystalline-amorphous composite superhard coating |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004074361A (en) * | 2002-08-20 | 2004-03-11 | Sumitomo Electric Ind Ltd | Coated hard tool |
| CN1654702A (en) * | 2005-02-16 | 2005-08-17 | 吴大维 | High oxidation resistance nanocrystalline-amorphous structured superhard composite film cutting tool and deposition method therefor |
| CN1804113A (en) * | 2006-01-19 | 2006-07-19 | 上海交通大学 | Method for preparing Ti-Si-N film by adjusting gas partial pressure of magnetic controlled sputtering reaction |
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| Title |
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| 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 20110815 杨莹泽 nc-TiN/a-Si3N4纳米复合薄膜的制备与性能研究 论文正文第38-39页 1-5 , 第8期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106906442A (en) * | 2015-12-23 | 2017-06-30 | 中国科学院宁波材料技术与工程研究所 | A kind of coating with high rigidity and self lubricity and preparation method thereof |
| CN106906442B (en) * | 2015-12-23 | 2019-05-10 | 中国科学院宁波材料技术与工程研究所 | A kind of coating and preparation method thereof with high rigidity and self-lubrication |
| CN109423613A (en) * | 2017-08-31 | 2019-03-05 | 南京理工大学 | The preparation method of corrosion-resistant decorating film zirconium nitride |
| CN112626519A (en) * | 2020-12-16 | 2021-04-09 | 蚌埠飞宇轴承有限公司 | Processing technology for bearing element for prolonging fatigue life of rolling bearing |
| CN113463023A (en) * | 2021-04-29 | 2021-10-01 | 华东师范大学 | Preparation method of silicon nitride composite film for surface abrasion resistance of medical instrument die |
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Application publication date: 20111214 |