CN111334794A - 一种在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜及方法 - Google Patents
一种在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜及方法 Download PDFInfo
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Abstract
本发明属于材料表面改性领域，具体涉及一种在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜及方法。采用等离子体增强非平衡磁控溅射物理气相沉积(PEUMS‑PVD)和等离子体增强化学气相沉积(PECVD)相结合技术于基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜。本发明改性膜，表面致密，耐磨、耐蚀性能良好，尤其适用于海洋大气腐蚀环境，在处于海洋大气环境的精密仪器、微型散热器等具有很好的防护效果。
Description
技术领域
本发明属于材料表面改性领域，具体涉及一种在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜及方法。
背景技术
铜是一种常用的导电、导热材料，但是在应用过程中存在强度低，易氧化，易磨损，耐腐性差等缺点。类金刚石薄膜(DLC)具备许多优异的性能，包括高硬度、高耐磨性、低摩擦系数、优良的化学惰性等。将DLC膜作为铜基体保护层，不仅可以提高铜基体的表面硬度、化学惰性，而且还不会降低基体的导热效率。但现阶段直接常用化学气相沉积法在铜基体上生长DLC膜有较大的困难。首先铜不是溶碳材料，DLC膜和铜基体的结合力小；其次DLC膜和铜基体的热膨胀系数相差较大，在冷却过程中易剥离、开裂。因此，为提高铜基体与DLC膜之间的结合强度，是现阶段实现基体高性能的主要目的。
发明内容
针对上述在铜基体上沉积DLC膜遇到的问题，本发明目的在于提供一种在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜及方法。
为实现上述目的，本发明采取以下技术方案：
一种在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜的制备方法，采用等离子体增强非平衡磁控溅射物理气相沉积(PEUMS-PVD)和等离子体增强化学气相沉积(PECVD)相结合技术于基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜。
进一步的说，采用等离子体增强非平衡磁控溅射物理气相沉积技术(PEUMS-PVD)，进行钛靶溅射，真空条件下于处理后的基体表面沉积Ti过渡层；而后，在Ti靶磁控溅射的同时真空下通入CH4和Ar，CH4/Ar流量比为3-4:1，在等离子增强非平衡磁控溅射物理气相沉积和化学气相沉积(PEUMS-PVD+PECVD)技术相结合下利用Ti与CH4发生反应，随着CH4和Ar通入量的增加于过渡层上沉积Ti掺杂DLC梯度膜；而后继续于真空下，通入CH4和Ar，CH4/Ar流量比为3-5:1，即于最外层生成类金刚石薄膜。
所述处理后的基体为基体抛光后依次采用丙酮、无水乙醇、去离子水对基体进行超声波清洗；清洗后采用氮气吹干，在3.0×10-3Pa真空条件下，等离子溅射清洗。
所述等离子溅射清洗为在10-3Pa真空条件下，通入氩气，在850W微波下，使氩离子在负250-400V偏压的作用下，对基体进行溅射清洗10-15min。
所述基体为铜基体。
具体为：
(1)采用不同型号的砂纸对金属基体进行水磨，然后采用砂磨膏抛光到镜面效果。
(2)化学清洗：分别采用丙酮、无水乙醇、去离子水对铜基体进行超声波清洗；
(3)清洗后的铜基体：采用氮气吹干，直接放进真空室；
(4)等离子溅射清洗：真空被抽至衬底真空10-3Pa后，通入氩气流量20sccm，打开微波源，功率达到850W时，在基片台上加负偏压(250-400V)并通入冷却水，使氩离子在负偏压的作用下，对铜片进行溅射清洗10-15min。
(5)Ti过渡层制备：采用等离子体增强非平衡磁控溅射物理气相沉积技术(PEUMS-PVD)，进行钛靶溅射，在铜基体上制备Ti过渡层；Ti靶功率250-300W，氩气流量30sccm，基片偏压100-200V，制备时间30min。
(6)Ti/Ti掺杂DLC梯度膜制备：Ti靶溅射同时，再通入CH4和Ar(Ar/CH4流量比为1/3-4)，利用等离子增强非平衡磁控溅射物理气相沉积和化学气相沉积(PEUMS-PVD+PECVD)技术相结合，制备Ti/Ti掺杂DLC梯度膜，形成梯度成分渐变层，通过控制Ar/CH4流量比所述的梯度成分渐变是，随着CH4的通入，由于CH4需在等离子中分解成中性原子和离子基团，使其才能与Ti发生反应。，随着反应的进行，部分CH4与Ti发生反应，生成TiC；还有部分CH4化学气相沉积生成DLC膜，即生成钛掺杂类金刚石薄膜，其中，Ti以TiC的形式与DLC共同存在；进而提高改性膜与基体之间的结合力；其中，Ti靶功率不变，基片偏压100-200V，制备时间30min。
(7)表层DLC膜制备：将Ti靶停止溅射，继续通入CH4和Ar(控制量范围)，CH4/Ar流量比为5-3:1，基片偏压100-200V，溅射时间30min，即于最外层生成DLC膜。
一种基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜，按所述方法于基体表面溅射沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜。
所述改性薄膜为在Ti过渡层和类金刚石薄膜之间形成成分渐变层，渐变层为随着CH4在等离子中分解与Ti发生反应Ti以TiC的形式，与类金刚石膜共生存在而形成梯度。
所述Ti过渡层的厚度为50-100纳米，钛掺杂类金刚石薄膜厚度为150-200nm,表层类金刚石膜厚度为50-100纳米。
本发明的有益效果在于：
本发明将等离子体增强非平衡磁控溅射物理气相沉积(PEUMS-PVD)和等离子体增强化学气相沉积(PECVD)技术相结合，在基体与DLC膜之间引入梯度过渡层，获得Ti/Ti掺杂类金刚石/类金刚石膜的三明治结构，Ti/Ti掺杂类金刚石缓冲了膜层之间的内应力，提高了附着力，其制备的Ti掺杂类金刚石为梯度成分渐变层，形成界面缓冲，改善了DLC膜与铜基体之间的结合力。经测试，DLC膜与铜基体之间的结合强度大于400mN。
附图说明
图1为本发明实施例获得Ti过渡层及钛掺杂类金刚石薄膜结构示意图。
图2为本发明实施例获得Ti掺杂DLC膜的拉曼光谱图。
图3为本发明实施例获得Ti掺杂DLC膜的XPS窄谱解谱图，其中图3a为C1s的XPS窄谱解谱，图3b为Ti2p的XPS窄谱解谱。
图4为本发明实施例获得Ti掺杂DLC膜的成分随溅射深度变化的曲线图。
具体实施方式
以下通过具体的实施例对本发明作进一步说明，有助于本领域的普通技术人员更全面的理解本发明，但不以任何方式限制本发明。
本发明将等离子体增强非平衡磁控溅射物理气相沉积(PEUMS-PVD)和等离子体增强化学气相沉积(PECVD)技术相结合，通过Ti靶溅射，引入Ti过渡层，Ti过渡层的引入，降低了铜基体的界面位垒，促进DLC膜成核，并缓和DLC膜与铜基体之间由于热膨胀差引起的热应力，大大提高薄膜的质量。
本发明采用类金刚石薄膜(Diamond-like carbon)具备许多优异的性能，包括高硬度、高耐磨性、低摩擦系数、化学惰性等。而后在铜上沉积一层类金刚石薄膜，不仅不会影响其散热效率，而且可以提高基体的硬度和耐磨性，提高其耐划伤和耐腐蚀性能。本发明采用等离子体复合沉积技术，通过制备Ti过渡层，在铜基体上成功制备了钛掺杂类金刚石薄膜，表面致密，耐磨、耐蚀性能良好，尤其适用于海洋大气腐蚀环境，在处于海洋大气环境的精密仪器、微型散热器等具有很好的防护效果。
实施例1：
一种在铜基体上沉积Ti过渡层及钛掺杂类金刚石薄膜的制备方法，其方法步骤如下：
(1)将工业纯铜(厚度2cm)切割成10mm×10mm的试样。首先将试样依次用600#、800#、1000#、2000#的砂纸逐级水磨，然后采用W5、W3.5的金刚石磨砂膏表面抛光到镜面效果。
(2)分别采用丙酮、无水乙醇、去离子水依次对上述抛光后铜基体进行超声波清洗10min；
(2)清洗后的铜基体，采用氮气吹干，直接放进真空室；
(3)真空被抽至衬底真空3.0×10-3Pa后，通入氩气，流量20sccm，打开微波源，功率达到850W时，在基片台上加负偏压400V并通入冷却水，使氩离子在负偏压的作用下，对铜片进行溅射清洗10min。
(4)溅射清洗后采用Ti靶溅射，在铜基体上制备形成Ti过渡层；其条件为：Ti靶功率300W，氩气流量30sccm，基片偏压200V，制备时间30min。
(5)固定Ti靶功率300W不变，通入CH4气体，调整Ar/CH4流量比为1/3，于过渡层上形成成分渐变的Ti掺杂DLC梯度膜(参见图4)，基片偏压200V，制备时间30min。
(6)Ti靶停止溅射，继续通入CH4和Ar，调整Ar/CH4流量比为1/4，制备DLC膜，基片偏压100V，溅射时间30min；即于铜基体上沉积Ti过渡层及钛掺杂类金刚石薄膜(参见图1)。
对上述铜基体上沉积Ti过渡层及钛掺杂类金刚石薄膜中的Ti掺杂DLC膜进行结构表征以及成分的检测：
1)采用Raman光谱对所制备的Ti掺杂DLC膜进行结构表征(参见图2)。
对上述实施例获得Ti掺杂DLC膜进行拉曼光谱测试，通过拉曼光谱进行拟合，由图2中拟合后的峰位图可见，在800cm-1和1800cm-1之间拉曼峰明显是由两个展宽峰组成，是典型的类金刚石膜结构，用高斯拟合法可以将其分为两个峰：D峰和G峰；由此可见在铜基体上制备Ti掺杂DLC膜。
2)Ti掺杂DLC膜成分表征：
通过X射线光电子能谱分析(XPS)方法对上述实施例获得Ti掺杂DLC膜成分进行测试(参见图3)，由图3膜样品表面C1s和Ti2p的XPS窄谱及其解谱可见，图3a中样品的C1s窄谱可以拟合为四个结合能不同的峰，其结合能分别为：281.92eV、283.68eV、284.84eV、287.12eV。C1s谱中结合能为281.92eV的峰，属于与TiC的信号；位于283.68eV的峰为sp2C＝C的信号峰，而结合能位于284.84eV的峰则与sp3C-C碳的信号峰相对应；最后，电子结合能位于287.12eV的峰对应于C＝O的结合能；图3b对Ti2p的窄谱进行解谱，可以得到分别位于454.95eV、456.00eV、458.50eV、461.19eV、464.370eV的五个峰。结合能位于454.95eV的峰是与C结合生成TiC的Ti2p3/2的峰；电子结合能为461.19eV的峰为TiC中Ti2p1/2的信号；位于456eV的峰是Ti的有机复合物的Ti2p3/2的峰；位于458.50eV的峰为Ti的氧化物TiO2；位于464.37eV的第五个峰，为TiO2中Ti2p1/2的信号。
以上表征结果表明，样品膜表面存在Ti元素；Ti以TiC结构形式存在于DLC膜中。
3)Ti掺杂DLC膜样品成分随溅射深度变化的曲线：
通过X射线光电子能谱分析(XPS)方法对上述实施例获得Ti掺杂DLC膜样品成分随溅射深度进行测试(参见图4)，由图4可以看出，在样品表层，几乎完全是DLC膜，伴随少量吸附氧气的C＝O键；随着深度的变化，自20nm左右处，就出现TiC峰，此时是TiC与DLC共存的状态；随着溅射深度的增大，TiC峰逐渐增强，大于150nm以后，DLC信号峰几乎消失，此时为TiC过渡结构。由以上检测结果可以看出，在Ti过渡层与表层DLC之间，存在成分梯度渐变的Ti掺杂DLC膜梯度过渡层，Ti以TiC的形式与DLC膜共生，极大的提高了各膜层之间的结合力，提高了改性膜制备的成功率。
Claims (8)
1.一种在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜的制备方法，其特征在于：采用等离子体增强非平衡磁控溅射物理气相沉积(PEUMS-PVD)和等离子体增强化学气相沉积(PECVD)相结合技术于基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜。
2.按权利要求1所述的在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜的制备方法，其特征在于：采用等离子体增强非平衡磁控溅射物理气相沉积技术(PEUMS-PVD)，进行钛靶溅射，真空条件下于处理后的基体表面沉积Ti过渡层；而后，在Ti靶磁控溅射的同时真空下通入CH4和Ar，CH4/Ar流量比为3-4:1，在等离子增强非平衡磁控溅射物理气相沉积和化学气相沉积(PEUMS-PVD+PECVD)技术相结合下利用Ti与CH4发生反应，随着CH4和Ar通入量的增加于过渡层上沉积Ti掺杂DLC梯度膜；而后继续于真空下，通入CH4和Ar，CH4/Ar流量比为3-5:1，即于最外层生成类金刚石薄膜。
3.按权利要求1所述的在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜的制备方法，其特征在于：所述处理后的基体为基体抛光后依次采用丙酮、无水乙醇、去离子水对基体进行超声波清洗；清洗后采用氮气吹干，在3.0×10-3Pa真空条件下，等离子溅射清洗。
4.按权利要求3所述的在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜的制备方法，其特征在于：所述等离子溅射清洗为在10-3Pa真空条件下，通入氩气，在850W微波下，使氩离子在负250-400V偏压的作用下，对基体进行溅射清洗10-15min。
5.按权利要求1-4任意一项所述的在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜的制备方法，其特征在于：所述基体为铜基体。
6.一种权利要求1所述方法在基体表面沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜，其特征在于：按权利要求1所述方法于基体表面溅射沉积含Ti过渡层及钛掺杂类金刚石的改性薄膜。
7.按权利要求6所述的含Ti过渡层及钛掺杂类金刚石薄膜，其特征在于：所述改性薄膜为在Ti过渡层和类金刚石薄膜之间形成成分渐变层，渐变层为随着CH4在等离子中分解与Ti发生反应Ti以TiC的形式，与类金刚石膜共生存在而形成梯度。
8.按权利要求6或7所述的Ti过渡层及钛掺杂类金刚石薄膜，其特征在于：所述Ti过渡层的厚度为50-100纳米，钛掺杂类金刚石薄膜厚度为150-200nm,表层类金刚石膜厚度为50-100纳米。
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