WO2019119646A1 - Method for improving binding force and tribological property of fullerene-like thin film - Google Patents
Method for improving binding force and tribological property of fullerene-like thin film Download PDFInfo
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- WO2019119646A1 WO2019119646A1 PCT/CN2018/077978 CN2018077978W WO2019119646A1 WO 2019119646 A1 WO2019119646 A1 WO 2019119646A1 CN 2018077978 W CN2018077978 W CN 2018077978W WO 2019119646 A1 WO2019119646 A1 WO 2019119646A1
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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
- C23C16/22—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
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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
- C23C16/517—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 a combination of discharges covered by two or more of groups C23C16/503 - C23C16/515
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- the invention belongs to the field of plasma enhanced chemical vapor deposition and relates to a method for improving the adhesion and tribological properties of a fullerene-like film.
- the solid ultra-slip film and technology is a big leap in the development of tribology. It is the new high point of research and application of solid lubricating materials. It is the key technology to solve the high energy consumption of high-tech cutting technology, break through the long life and stability of equipment, and reduce equipment energy. Consumption and resource consumption.
- the fullerene-like film has a combination of high hardness, high modulus of elasticity, good chemical inertness, low friction coefficient, strong abrasion resistance, and excellent electrical properties, and is suitable as a protective coating. Moreover, the fullerene-like film can be deposited on the surface of various substrates at relatively low temperatures, and thus has broad application prospects in the fields of electrochemistry, mechanics, tribology, nuclear energy, aerospace and the like.
- fullerene-like films there has always been a major problem in the development and application of fullerene-like films.
- the adhesion between the fullerene-like film and the metal substrate is poor, it is easy to fall off from the metal substrate, and the friction coefficient is not particularly low, which is very
- the promotion and application of fullerene-like films are limited to a large extent.
- the other reason for the weak bonding is that the film generates extremely high stress during the preparation process, and the film itself is chemically inert, making it difficult to form a chemical bond with the metal substrate; and, as the thickness of the film increases, The bonding strength of the film to the metal substrate is lowered.
- the invention utilizes a plasma enhanced chemical vapor deposition method to dope N element and P element into a fullerene-like film, and the fullerene-like film has high hardness, high elastic modulus, good chemical inertness, low friction coefficient and anti-wear.
- the comprehensive properties such as strong properties and excellent electrical properties are further improved, which can effectively improve the bonding force between the film and the substrate, and further improve the tribological properties.
- the method has the advantages of simple equipment, low deposition temperature, good repeatability, and extremely low friction coefficient, and the adhesion between the substrate and the fullerene-like film is improved.
- a method for improving the adhesion and tribological properties of a fullerene-like film characterized in that the specific steps are:
- the pre-cleaned substrate is ultrasonically washed in acetone and ethanol for 20 to 40 minutes, and then dried by washing the ear;
- the mechanical pump, the Roots pump and the molecular pump are used to sequentially evacuate the chamber until the vacuum in the chamber is less than 1.0 ⁇ 10 -3 Pa; the molecular pump is turned off, the argon gas is introduced into the chamber, and the pulse bias is -700 to -500 V, Plasma cleaning is carried out for 30 minutes under a condition of a duty ratio of 50 to 70% to remove impurities and contaminants remaining on the surface;
- a mixed gas of nitrogen, phosphine and methane is introduced, and the film is deposited for 1 to 3 hours under the conditions of a pulse bias of -700 to -400 V, a deposition pressure of about 20 to 50 Pa, and a duty ratio of 50 to 60%.
- Both the diameter and the height are 200 to 450 mm, and the diameter of the upper plate and the diameter of the lower plate are 200 to 500 mm, and the distance between them is about 30 to 100 mm.
- the volume flow rate of the argon gas in the step 3) is 50 to 280 SCCM.
- the volume flow rate of the nitrogen gas, the phosphine gas, and the methane in the step 4) is 20 to 50 SCCM, 10 to 30 SCCM, and 5 to 30 SCCM, respectively.
- the power supplies used are RF power and pulsed power instead of conventional single RF power.
- the RF power supply can control the density of the plasma
- the DC negative bias can control the energy of the plasma
- the pulse power supply can reduce the internal stress generated by the fullerene-like film. The combination of the three has achieved excellent results.
- the substrate is stainless steel, ceramic, polymeric material or composite material.
- the invention utilizes plasma enhanced chemical vapor deposition technology to deposit a fullerene film co-doped with N and P elements on the substrate, and the method has the advantages of simple process, high economic efficiency, low deposition temperature and good repeatability. It can greatly improve the bonding force and tribological properties of the fullerene-like film, and make the fullerene-like film have better lubrication effect. Therefore, the invention has a wide range of applications and plays an important role in various substrate surfaces requiring lubrication.
- the binding force and tribological properties of the substrate of the present invention and the fullerene-like carbon film are greatly improved, and the working life of the fullerene-like film under high-intensity working conditions is improved.
- Figure 1 is a graph showing the friction coefficient of a fullerene-like film co-doped with N and P elements and a raw fullerene film.
- Figure 2 is a graph showing the binding force of a fullerene-like film co-doped with N and P elements and a raw fullerene film.
- the present invention proposes a method for improving the adhesion and tribological properties of a fullerene-like film, and the present invention will be further described below.
- a mixed gas of nitrogen (30 SCCM), phosphine (10 SCCM) and methane (10 SCCM) is introduced, and the gas pressure is adjusted to about 35 Pa, and the temperature is lowered at a pulse bias of -500 V and a duty ratio of 50%.
- a fullerene film was deposited and deposited for 2 hours.
- the average coefficient of friction of the fullerene film co-doped with N and P elements is 0.012
- the average coefficient of friction of the fullerene film not doped with N and P elements is 0.021.
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Abstract
Provided is a method for improving the binding force and tribological property of a fullerene-like thin film, comprising: 1) cleaning a substrate; 2) loading a sample; 3) evacuating and re-cleaning; and 4) depositing a fullerene-like thin film. The method uses a plasma-enhanced chemical vapor deposition technique, wherein nitrogen, phosphine and methane are used as gas sources, and the fullerene-like thin film is deposited onto a substrate under the combined action of a radio frequency power source and a pulsed negative bias. The process of the method is simple, economic and efficient, the deposition temperature is low, the repeatability is good, the friction coefficient is extremely low, the improvement in the binding force of the substrate to the fullerene-like thin film is obvious, and the binding force and tribological property of the fullerene-like thin film can thus be substantially improved. The method is applicable to a substrate such as a stainless steel surface, a ceramic, a high polymer material and a composite material, and has broad application prospects.
Description
本发明属于等离子增强化学气相沉积领域,涉及一种提高类富勒烯薄膜结合力和摩擦学性能的方法。The invention belongs to the field of plasma enhanced chemical vapor deposition and relates to a method for improving the adhesion and tribological properties of a fullerene-like film.
随着机械系统的高精密化、高集成化、高能效化、高可靠性发展,机械系统运动部件的表面效应和界面效应越来越突出,对于摩擦磨损性能的控制要求也越来越苛刻。发达国家每年因摩擦磨损造成的损失约占国民生产总值(GDP)的5%-7%。我国是制造大国,其损失比例更高。据不完全统计,我国每年由于摩擦磨损造成的经济损失达上万亿元。与工业发达国家相比,我国机械装备使用寿命短、资源能源浪费巨大。参照2012年的统计数据,我国单位GDP能耗是日本的7倍,美国的3.3倍,世界平均水平的2.5倍。减少机械运动部件摩擦磨损已被视为有效延长其工作寿命并提高其运行的可靠性、稳定性途径之一。而固体超滑薄膜与技术是摩擦学发展的一个大跨越,是固体润滑材料研究与应用的新高点,是解决高新尖技术高能耗、突破设备长寿命和稳定性的关键技术,同时降低设备能耗和资源消耗。而类富勒烯薄膜具有高硬度、高弹性模量、好化学惰性、低摩擦系数、抗磨性强、电学特性优异等综合性能,很适合作为保护涂层。而且,类富勒烯薄膜可以在比较低的温度下沉积在各种基底的表面,因此在电化学、机械、摩擦学、核能、航空航天等领域具有广泛的应用前景。With the high precision, high integration, high energy efficiency and high reliability development of mechanical systems, the surface effects and interface effects of moving parts of mechanical systems are becoming more and more prominent, and the control requirements for friction and wear performance are becoming more and more demanding. The annual losses due to friction and wear in developed countries account for about 5%-7% of gross national product (GDP). China is a big manufacturing country with a higher proportion of losses. According to incomplete statistics, the annual economic losses caused by friction and wear in China have reached trillions of yuan. Compared with industrial developed countries, China's mechanical equipment has a short service life and huge waste of resources and energy. According to the statistics of 2012, China's energy consumption per unit of GDP is seven times that of Japan, 3.3 times that of the United States, and 2.5 times the world average. Reducing friction and wear of mechanical moving parts has been recognized as one of the ways to effectively extend its working life and improve the reliability and stability of its operation. The solid ultra-slip film and technology is a big leap in the development of tribology. It is the new high point of research and application of solid lubricating materials. It is the key technology to solve the high energy consumption of high-tech cutting technology, break through the long life and stability of equipment, and reduce equipment energy. Consumption and resource consumption. The fullerene-like film has a combination of high hardness, high modulus of elasticity, good chemical inertness, low friction coefficient, strong abrasion resistance, and excellent electrical properties, and is suitable as a protective coating. Moreover, the fullerene-like film can be deposited on the surface of various substrates at relatively low temperatures, and thus has broad application prospects in the fields of electrochemistry, mechanics, tribology, nuclear energy, aerospace and the like.
然而类富勒烯薄膜发展和应用中一直存在一个重大的难题,类富勒烯薄膜与金属基底之间结合力较差,很容易从金属基体上脱落,且摩擦系数不是特别低,这在很大程度上限制了类富勒烯薄膜的推广应用。导致弱结合力而别的原因是由于薄膜在制备过程中产生了极高的应力,加之薄膜本身就具有化学惰性,很难与金属基底形成化学键合;并且,随着薄膜厚度的增加,更使得薄膜与金属基底结合强度降低。制备类富勒烯薄膜的方法很多,而如何增强金属基底与类富勒烯薄膜结合力并减小摩擦力是关键问题。目前,各国科学家和产业界人士已尝试通过添加梯度过渡层来增加碳薄膜与钢基底间结合力(专利ZL 200910098622.1), 但此方法工艺复杂,且对于结合力的提升效果并不明显。此外,所沉积的类富勒烯薄膜摩擦系数较高(专利ZL 200710308591.9)。However, there has always been a major problem in the development and application of fullerene-like films. The adhesion between the fullerene-like film and the metal substrate is poor, it is easy to fall off from the metal substrate, and the friction coefficient is not particularly low, which is very The promotion and application of fullerene-like films are limited to a large extent. The other reason for the weak bonding is that the film generates extremely high stress during the preparation process, and the film itself is chemically inert, making it difficult to form a chemical bond with the metal substrate; and, as the thickness of the film increases, The bonding strength of the film to the metal substrate is lowered. There are many methods for preparing fullerene-like films, and how to enhance the adhesion of metal substrates to fullerene-like films and reduce friction is a key issue. At present, scientists and industrialists in various countries have tried to increase the bonding force between the carbon film and the steel substrate by adding a gradient transition layer (patent ZL 200910098622.1), but the method is complicated and the effect of improving the bonding force is not obvious. In addition, the deposited fullerene-like film has a high coefficient of friction (patent ZL 200710308591.9).
目前大家都关注于制备类富勒烯薄膜,并未通过掺杂元素进而改善类富勒烯薄膜。At present, everyone is concerned about the preparation of fullerene-like films, which do not improve the fullerene-like films by doping elements.
综上所述,研究类富勒烯薄膜的制备以及普适化具有重要的科学意义和应用前景。In summary, the preparation of the fullerene film and its universalization have important scientific significance and application prospects.
发明内容Summary of the invention
本发明的目的在于提供一种提高类富勒烯薄膜结合力和摩擦学性能的方法。It is an object of the present invention to provide a method for improving the adhesion and tribological properties of a fullerene-like film.
本发明利用等离子体增强化学气相沉积方法将N元素和P元素掺杂于类富勒烯薄膜,将类富勒烯薄膜具有高硬度、高弹性模量、好化学惰性、低摩擦系数、抗磨性强、电学特性优异等综合性能得到更进一步提升,能够有效改善薄膜和基底的结合力,进一步提升摩擦学性能。并且此方法设备简单,沉积温度低,重复性好,摩擦系数极低,基底与类富勒烯薄膜结合力提升效果明显。The invention utilizes a plasma enhanced chemical vapor deposition method to dope N element and P element into a fullerene-like film, and the fullerene-like film has high hardness, high elastic modulus, good chemical inertness, low friction coefficient and anti-wear. The comprehensive properties such as strong properties and excellent electrical properties are further improved, which can effectively improve the bonding force between the film and the substrate, and further improve the tribological properties. Moreover, the method has the advantages of simple equipment, low deposition temperature, good repeatability, and extremely low friction coefficient, and the adhesion between the substrate and the fullerene-like film is improved.
一种提高类富勒烯薄膜结合力和摩擦学性能的方法,其特征在于具体步骤为:A method for improving the adhesion and tribological properties of a fullerene-like film, characterized in that the specific steps are:
1)清洗基底1) Cleaning the substrate
将预先清洁后的基底放入丙酮、乙醇中超声清洗各20~40分钟,然后用洗耳球吹干;The pre-cleaned substrate is ultrasonically washed in acetone and ethanol for 20 to 40 minutes, and then dried by washing the ear;
2)装入样品2) Loading the sample
将清洗后的样品转移至真空腔,放置在下部的基底盘上,基底盘和脉冲负偏压电源相连;Transferring the cleaned sample to a vacuum chamber, placed on a lower substrate tray, and the substrate tray is connected to a pulsed negative bias power source;
3)抽真空并再次清洗3) Vacuum and clean again
利用机械泵、罗茨泵和分子泵依次将腔内抽真空,直至腔内真空小于1.0×10
-3Pa;关闭分子泵,腔内通入氩气,在脉冲偏压-700~-500V,占空比50~70%的条件下进行等离子体清洗30分钟,用以去除表面残留的杂质和污染物;
The mechanical pump, the Roots pump and the molecular pump are used to sequentially evacuate the chamber until the vacuum in the chamber is less than 1.0×10 -3 Pa; the molecular pump is turned off, the argon gas is introduced into the chamber, and the pulse bias is -700 to -500 V, Plasma cleaning is carried out for 30 minutes under a condition of a duty ratio of 50 to 70% to remove impurities and contaminants remaining on the surface;
4)沉积类富勒烯薄膜4) Deposited fullerene film
通入氮气、磷化氢、甲烷组成的混合气体,在脉冲偏压-700~-400V、沉积气压约20~50Pa、占空比50~60%的条件下沉积薄膜1~3小时,真空室直径和高 度都为200~450mm,上极板直径和下极板直径为200~500mm,它们之间的距离约为30~100mm。A mixed gas of nitrogen, phosphine and methane is introduced, and the film is deposited for 1 to 3 hours under the conditions of a pulse bias of -700 to -400 V, a deposition pressure of about 20 to 50 Pa, and a duty ratio of 50 to 60%. Both the diameter and the height are 200 to 450 mm, and the diameter of the upper plate and the diameter of the lower plate are 200 to 500 mm, and the distance between them is about 30 to 100 mm.
步骤3)中所述氩气的体积流量为50~280SCCM。The volume flow rate of the argon gas in the step 3) is 50 to 280 SCCM.
步骤4)中所述氮气、磷化氢、甲烷的体积流量依次为20~50SCCM、10~30SCCM、5~30SCCM。The volume flow rate of the nitrogen gas, the phosphine gas, and the methane in the step 4) is 20 to 50 SCCM, 10 to 30 SCCM, and 5 to 30 SCCM, respectively.
所用的电源为射频电源和脉冲电源而非常规的单一射频电源。在此系统里,射频电源能控制等离子体的密度,直流负偏压能控制等离子体的能量以及脉冲电源能够减小类富勒烯薄膜产生的内应力,三者结合已达到优异的效果。The power supplies used are RF power and pulsed power instead of conventional single RF power. In this system, the RF power supply can control the density of the plasma, the DC negative bias can control the energy of the plasma, and the pulse power supply can reduce the internal stress generated by the fullerene-like film. The combination of the three has achieved excellent results.
所述基底为不锈钢、陶瓷、高分子材料或复合材料。The substrate is stainless steel, ceramic, polymeric material or composite material.
本发明利用等离子体增强化学气相沉积技术对基底沉积共掺杂N和P元素的类富勒烯薄膜,此方法具有工艺简单、经济高效、沉积温度低、重复性好等优势。能够大幅度提升类富勒烯薄膜的结合力和摩擦学性能,使类富勒烯薄膜起到更好的润滑效果。因此,用于各种需要润滑的基底表面,该发明应用背景广泛且发挥着重要的作用。The invention utilizes plasma enhanced chemical vapor deposition technology to deposit a fullerene film co-doped with N and P elements on the substrate, and the method has the advantages of simple process, high economic efficiency, low deposition temperature and good repeatability. It can greatly improve the bonding force and tribological properties of the fullerene-like film, and make the fullerene-like film have better lubrication effect. Therefore, the invention has a wide range of applications and plays an important role in various substrate surfaces requiring lubrication.
本发明基底与类富勒烯碳薄膜结合力和摩擦学性能大幅度提高,提升类富勒烯薄膜在高强度工况环境下的工作寿命。The binding force and tribological properties of the substrate of the present invention and the fullerene-like carbon film are greatly improved, and the working life of the fullerene-like film under high-intensity working conditions is improved.
图1是共掺杂N和P元素的类富勒烯薄膜与原始类富勒烯薄膜摩擦系数对比图。Figure 1 is a graph showing the friction coefficient of a fullerene-like film co-doped with N and P elements and a raw fullerene film.
图2是共掺杂N和P元素的类富勒烯薄膜与原始类富勒烯薄膜结合力对比图。Figure 2 is a graph showing the binding force of a fullerene-like film co-doped with N and P elements and a raw fullerene film.
本发明提出了一种提高类富勒烯薄膜结合力和摩擦学性能的方法,下面对本发明作进一步说明。The present invention proposes a method for improving the adhesion and tribological properties of a fullerene-like film, and the present invention will be further described below.
实施例1:Example 1:
首先选择表面光洁的不锈钢片三片,用稀盐酸溶液预清洗,等其干燥后再将其放入丙酮、乙醇中超声清洗各30分钟,取出不锈钢片,用洗耳球吹干后迅速转入真空腔基底上,开始抽真空。其次,待真空抽到小于1.0×10
-3Pa时,通入氩气(150SCCM),调整气压约为25Pa,在脉冲偏压-600V、占空比为50%的情 况下,进行等离子体清洗,持续30分钟。清洗完成后,通入氮气(30SCCM)、磷化氢(10SCCM)和甲烷(10SCCM)组成的混合气体,调节气压约为35Pa,在脉冲偏压-500V、占空比50%的条件下进行低温沉积类富勒烯薄膜,沉积时间为2小时。
First, select three pieces of stainless steel with smooth surface, pre-clean with dilute hydrochloric acid solution, wait for it to dry, then put it into acetone and ethanol for ultrasonic cleaning for 30 minutes, take out the stainless steel piece, dry it with ear-washing ball and quickly transfer it. On the vacuum chamber substrate, vacuuming begins. Next, when the vacuum is drawn to less than 1.0×10 -3 Pa, argon gas (150 SCCM) is introduced, the gas pressure is adjusted to about 25 Pa, and the plasma is cleaned under the pulse bias of -600 V and the duty ratio is 50%. , lasts for 30 minutes. After the cleaning is completed, a mixed gas of nitrogen (30 SCCM), phosphine (10 SCCM) and methane (10 SCCM) is introduced, and the gas pressure is adjusted to about 35 Pa, and the temperature is lowered at a pulse bias of -500 V and a duty ratio of 50%. A fullerene film was deposited and deposited for 2 hours.
实施例2:Example 2:
首先选择表面光洁的硅片两片,其中一片表面沉积共掺杂N和P元素的类富勒烯薄膜,另外一片表面沉积不掺杂N和P元素的类富勒烯薄膜。然后对这两片表面沉积碳薄膜的硅基底进行摩擦试验。试验条件为:对偶球6mm钢球,载荷10N,频率3Hz,振幅5mm,时间1小时。正如图1所示,共掺杂N和P元素的类富勒烯薄膜的平均摩擦系数为0.012,而不掺杂N和P元素的类富勒烯薄膜的平均摩擦系数为0.021。重复三次实验,确保实验结果的准确性,表明共掺杂N和P元素的类富勒烯薄膜可以大幅度降低摩擦力,摩擦力下降约43%。First, two wafers with a smooth surface were selected. One surface was deposited with a fullerene film co-doped with N and P elements, and the other surface was deposited with a fullerene film not doped with N and P elements. The two silicon substrates on which the carbon film was deposited were then subjected to a rubbing test. The test conditions were as follows: a dual ball 6 mm steel ball with a load of 10 N, a frequency of 3 Hz, an amplitude of 5 mm, and a time of 1 hour. As shown in Fig. 1, the average coefficient of friction of the fullerene film co-doped with N and P elements is 0.012, and the average coefficient of friction of the fullerene film not doped with N and P elements is 0.021. Three experiments were repeated to ensure the accuracy of the experimental results, indicating that the fullerene film co-doped with N and P elements can greatly reduce the friction and reduce the friction by about 43%.
实施例3:Example 3:
首先选择表面光洁的两片不锈钢片,其中一片表面沉积共掺杂N和P元素的类富勒烯薄膜,另外一片表面沉积不掺杂N和P元素的类富勒烯薄膜。然后对这两片表面沉积碳薄膜的硅基底进行划痕试验。正如图2所示,共掺杂N和P元素的类富勒烯薄膜的结合力为40N,而不掺杂N和P元素的类富勒烯薄膜的结合力为10N。重复三次实验,确保实验结果的准确性,表明共掺杂N和P元素的类富勒烯薄膜可以提高基底与类富勒烯薄膜结合力,将结合力提升300%。First, two stainless steel sheets with a smooth surface were selected. One surface was deposited with a fullerene film co-doped with N and P elements, and the other surface was deposited with a fullerene film not doped with N and P elements. The two silicon substrates on which the carbon film was deposited were then subjected to a scratch test. As shown in FIG. 2, the fullerene film co-doped with N and P elements has a bonding force of 40 N, and the fullerene film without N and P elements has a bonding strength of 10 N. Three experiments were repeated to ensure the accuracy of the experimental results, indicating that the fullerene film co-doped with N and P elements can improve the adhesion of the substrate to the fullerene-like film and increase the bonding force by 300%.
Claims (5)
- 一种提高类富勒烯薄膜结合力和摩擦学性能的方法,其特征在于具体步骤为:A method for improving the adhesion and tribological properties of a fullerene-like film, characterized in that the specific steps are:1)清洗基底1) Cleaning the substrate将预先清洁后的基底放入丙酮、乙醇中超声清洗各20~40分钟,然后用洗耳球吹干;The pre-cleaned substrate is ultrasonically washed in acetone and ethanol for 20 to 40 minutes, and then dried by washing the ear;2)装入样品2) Loading the sample将清洗后的样品转移至真空腔,放置在下部的基底盘上,基底盘和脉冲负偏压电源相连;Transferring the cleaned sample to a vacuum chamber, placed on a lower substrate tray, and the substrate tray is connected to a pulsed negative bias power source;3)抽真空并再次清洗3) Vacuum and clean again利用机械泵、罗茨泵和分子泵依次将腔内抽真空,直至腔内真空小于1.0×10 -3Pa;关闭分子泵,腔内通入氩气,在脉冲偏压-700~-500V,占空比50~70%的条件下进行等离子体清洗30分钟; The mechanical pump, the Roots pump and the molecular pump are used to sequentially evacuate the chamber until the vacuum in the chamber is less than 1.0×10 -3 Pa; the molecular pump is turned off, the argon gas is introduced into the chamber, and the pulse bias is -700 to -500 V, Plasma cleaning for 30 minutes under a condition of a duty ratio of 50 to 70%;4)沉积类富勒烯薄膜4) Deposited fullerene film通入氮气、磷化氢、甲烷组成的混合气体,在脉冲偏压-700~-400V、沉积气压约20~50Pa、占空比50~60%的条件下沉积薄膜1~3小时,真空室直径和高度都为200~450mm,上极板直径和下极板直径为200~500mm,它们之间的距离约为30~100mm。A mixed gas of nitrogen, phosphine and methane is introduced, and the film is deposited for 1 to 3 hours under the conditions of a pulse bias of -700 to -400 V, a deposition pressure of about 20 to 50 Pa, and a duty ratio of 50 to 60%. Both the diameter and the height are 200 to 450 mm, and the diameter of the upper plate and the diameter of the lower plate are 200 to 500 mm, and the distance between them is about 30 to 100 mm.
- 如权利要求1所述的方法,其特征在于步骤3)中所述氩气的体积流量为50~280SCCM。The method of claim 1 wherein said argon gas has a volumetric flow rate of from 50 to 280 SCCM in step 3).
- 如权利要求1所述的方法,其特征在于步骤4)中所述氮气、磷化氢、甲烷的体积流量依次为20~50SCCM、10~30SCCM、5~30SCCM。The method according to claim 1, wherein the volume flow rate of the nitrogen gas, the phosphine gas, and the methane in the step 4) is 20 to 50 SCCM, 10 to 30 SCCM, and 5 to 30 SCCM, respectively.
- 如权利要求1所述的方法,其特征在于所用的电源为射频电源和脉冲电源。The method of claim 1 wherein the power source used is a radio frequency power source and a pulse power source.
- 如权利要求1所述的方法,其特征在于所述基底为不锈钢、陶瓷、高分子材料或复合材料。The method of claim 1 wherein said substrate is stainless steel, ceramic, polymeric material or composite material.
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