CN104498874B - 低气氛敏感性掺杂非晶碳基薄膜及其制备方法 - Google Patents

低气氛敏感性掺杂非晶碳基薄膜及其制备方法 Download PDF

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CN104498874B
CN104498874B CN201410749907.8A CN201410749907A CN104498874B CN 104498874 B CN104498874 B CN 104498874B CN 201410749907 A CN201410749907 A CN 201410749907A CN 104498874 B CN104498874 B CN 104498874B
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吴行阳
邓兆星
张建华
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Abstract

本发明涉及一种低气氛敏感性掺杂非晶碳基薄膜及其制备方法。该薄膜主要由碳元素和缺电子掺杂元素经气相沉积得到，其中所述缺电子掺杂元素的原子数含量不超过10%。本发明在常见非晶碳基薄膜中掺入该类元素中的一种或两种及以上，或同时掺入其它常见的共掺杂元素，此时，缺电子掺杂元素和共掺杂元素的总含量不超过40%以增加缺电子掺杂元素的反应性和稳定性。缺电子元素的存在可在一定程度上吸引碳原子周围的电子，降低碳原子周围成键电子之间以及碳原子周围电子与环境成分和相接触材料表面间的相互作用，从而降低摩擦及其对环境气氛的敏感性，减少磨损。本发明的掺杂非晶碳基薄膜沉积于常见固体材料部件表面，主要用于部件的表面保护、润滑等领域。

Description

低气氛敏感性掺杂非晶碳基薄膜及其制备方法
技术领域
本发明涉及一种掺杂非晶碳基薄膜及其掺杂方法，特别是一种低气氛敏感性掺杂非晶碳基薄膜及其掺杂方法。
背景技术
非晶碳基薄膜(类金刚石膜)在水中具有低摩擦、低磨损和优异的耐腐蚀性，以水润滑替代传统的油润滑，在节约能源资源、保护环境方面具有重要的经济和社会意义，是理想的表面保护自润滑材料。然而，现有非晶碳基薄膜在空气中的摩擦系数较高且不稳定，特别是受空气湿度的影响较大，在发生水泄露或水供给出现问题时不能起到稳定润滑的作用。为了实现水或空气等多种气氛中稳定、有效的润滑，提高机械的运行稳定性并降低润滑成本，有必要开发一种在不同湿度空气和水中均具有低且稳定的摩擦系数、耐磨损的非晶碳基薄膜。
从近年来国内外的研究成果来看，非晶碳基薄膜的摩擦系数主要取决于悬挂键与对偶的相互作用。在沉积过程中非晶碳基薄膜内部会发生碳链或环的扭曲，使相邻成键电子对间的距离变小，这样相邻电子对之间的排斥力增大，导致薄膜内部往往存在较大的内应力。另一方面，在摩擦过程中，随着薄膜表面的磨损，表面碳原子将形成悬挂键，由于内部成键电子对之间较大的排斥力作用，使内部电子部分偏移至悬挂键，从而增强悬挂键作为供电子基的反应活性，悬挂键与对偶摩擦面形成悬键咬合作用，使摩擦力增大。同时，悬挂键对周围气氛极为敏感的特性也使得该类薄膜的摩擦学特性因气氛而变化，特别是空气中的摩擦系数较高且不稳定，薄膜对气氛环境的变化缺乏自适应性，应用范围受到限制。
发明内容
本发明的目的之一在于提供一种低气氛敏感性掺杂非晶碳基薄膜，以提高薄膜的自适应性。
本发明的目的之二在于提供该非晶碳基薄膜的制备方法。
为达到上述目的，本发明的构思是：在薄膜中掺入掺杂元素以降低碳悬挂键与对偶的相互作用，从而降低薄膜配副在摩擦过程中对气氛的敏感性，在不同环境中均可得到低且稳定的摩擦系数。通过在类金刚石薄膜中掺入掺杂元素，促使薄膜内部电子向掺杂元素原子迁移，就可降低相邻电子对之间的排斥力及薄膜的内应力，降低悬挂键作为供电子基的反应活性，钝化悬挂键，最终降低摩擦副间的摩擦力及其对环境的敏感程度。
根据上述构思，本发明采用如下技术方案：
一种低气氛敏感性掺杂非晶碳基薄膜，其特征在于该薄膜主要由碳元素和掺杂元素经气相沉积得到，其中所述掺杂元素的原子数含量不超过10％。
上述的掺杂元素为铟、镓、锡、镝、锗、铋中的至少一种。
上述的薄膜中还掺杂氢、硅、氮、氧、硼、铬、钛、铝、铜、锰、锌、钼、钨、铁、镍、钴、银、钒、锆、碲、硒、氟、氯、溴、硫、磷中的至少一种共掺杂元素，所述的掺杂元素和共掺杂元素的总原子数含量不超过40％。
一种制备上述的低气氛敏感性掺杂非晶碳基薄膜的方法，其特征在于该方法的具体步骤为：在利用现有的沉积法进行非晶碳基薄膜制备的同时，采用掺杂元素的纯金属、合金或有机络合物，通过物理气相法进行掺杂薄膜的制备。
上述的物理气相法为：溅射法、加热蒸发法或激光蒸发法。
上述的溅射法时溅射气体的分压不超过3Pa，加在基体上的负偏压范围为0-200V。
上述的采用所述的加热蒸发或激光蒸发法进行掺杂时，负偏压范围为0-350V。
上述的导入掺杂元素的有机络合物进行掺杂时，掺杂元素有机络合物的分压为0.01-10Pa。
一种制备上述的低气氛敏感性掺杂非晶碳基薄膜的方法，其特征在于在利用现有的沉积法进行非晶碳基薄膜制备的同时，采用掺杂元素的纯金属、合金或有机络合物，通过物理气相法进行掺杂薄膜的制备，同时导入氮气、氧气、有机化合物或络合物中的一种或两种及以上的共掺杂反应性气体，以增加掺杂元素在基体表面的反应性和稳定性，共掺杂反应性气体的分压为0.01-10Pa。
由于铟、镓、锡、镝、锗、铋等元素在发光二极管中作为空穴材料使用较广。本发明在常见非晶碳基薄膜中掺入该类元素中的一种或两种及以上，在一定程度上吸引碳原子周围的电子，降低碳原子周围成键电子之间以及碳原子周围电子与环境成分和相接触材料表面间的相互作用，从而降低摩擦及其对环境气氛的敏感性，减少磨损。本发明的掺杂非晶碳基薄膜沉积于常见固体材料部件表面，主要用于部件的表面保护、润滑等领域。
具体实施方式
作为具体实施例，本发明采用如下三种制备方法。
实施例一：采用溅射和反应溅射的物理气相沉积法，结合化学气相沉积法进行沉积。即选用铟为靶材，0.05-3Pa的氩气为溅射气体进行溅射沉积的同时，导入0.05-10Pa的碳源和共掺杂源混合反应性气体六甲基二硅氧烷和甲苯，沉积过程中基体上始终施加有射频功率进行射频化学气相沉积，负偏压为
0-200V，所得薄膜为硅、氢、氧和铟的共掺杂非晶碳基薄膜，在水和空气中的摩擦系数均约为0.05，对环境气氛的依赖程度低。
实施例二：基本方法同实施例一，不同之处在于在沉积过程中同时导入0.01-3Pa的氮气，获得氮、氢、硅、氧和铟的共掺杂非晶碳基薄膜。
实施例三：基本方法同实施例一，不同之处在于基体上施加的是直流偏压，负偏压为0-200V，沉积过程中没有引入化学气相沉积技术，即只采用物理气相沉积法进行掺杂薄膜的沉积。
实施例四：选用铟和石墨为靶材，氩气为溅射气体，采用多靶溅射进行掺杂薄膜的物理气相沉积，氩气分压为0.05-3Pa，。
实施例五：基本方法同实施例四，不同之处在于在沉积过程中导入0.01-3Pa的氮气，可获得氮和铟共掺杂非晶碳基薄膜。
实施例六：导入0.05-10Pa的甲苯为碳源气体，0.05-10Pa的六甲基二硅氧烷为共掺杂气体，0.05-10Pa的三甲基铟为掺杂元素源，采用等离子增强化学气相沉积法进行掺杂薄膜的制备，基体上施加0-350V的直流负偏压，所得薄膜为氢、氧、硅和铟的共掺杂非晶碳基薄膜。

Claims (7)

1.一种低气氛敏感性掺杂非晶碳基薄膜，其特征在于该薄膜主要由碳元素和掺杂元素经气相沉积得到，其中所述掺杂元素的原子数含量不超过10%;
所述的掺杂元素为铟、镓、锡、镝、铋中的至少一种;
所述的薄膜中还掺杂氢、硅、氮、氧、硼、铬、钛、铝、铜、锰、锌、钼、钨、铁、镍、钴、银、钒、锆、碲、硒、氟、氯、溴、硫、磷中的至少一种共掺杂元素，所述的掺杂元素和共掺杂元素的总原子数含量不超过40%。
2.一种制备根据权利要求1所述的低气氛敏感性掺杂非晶碳基薄膜的方法，其特征在于该方法的具体步骤为：在利用现有的沉积法进行非晶碳基薄膜制备的同时，采用掺杂元素的纯金属、合金或有机络合物，通过物理气相法进行掺杂薄膜的制备。
3.根据权利要求2所述的方法，其特征在于所述的物理气相法为：溅射法、加热蒸发法或激光蒸发法。
4.根据权利要求3所述的方法，其特征在于所述的溅射法时溅射气体的分压不超过3Pa，加在基体上的负偏压范围为0-200V。
5.根据权利要求3所述的方法，其特征在于采用所述的加热蒸发或激光蒸发法进行掺杂时，负偏压范围为0-350V。
6.根据权利要求2所述的方法，其特征在于所述的导入掺杂元素的有机络合物进行掺杂时，掺杂元素有机络合物的分压为0.01-10Pa。
7.一种制备根据权利要求2所述的低气氛敏感性掺杂非晶碳基薄膜的方法，其特征在于在利用现有的沉积法进行非晶碳基薄膜制备的同时，采用掺杂元素的纯金属、合金或有机络合物，通过物理气相法进行掺杂薄膜的制备，同时导入氮气、氧气、有机化合物或络合物中的一种或两种及以上的共掺杂反应性气体，以增加掺杂元素在基体表面的反应性和稳定性，共掺杂反应性气体的分压为0.01-10Pa。
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