以a-C:H为代表的类金刚石（DLC）固体润滑碳膜可实现宏观超滑特性，在真空和宽温域等极端工况条件下具有潜在应用前景。然而不同于二维材料，磨合阶段是实现DLC碳膜超滑的重要前提，其中涉及一系列复杂的界面摩擦化学反应。理解摩擦化学诱导摩擦演化的动力学机制，对进一步认识DLC碳膜超滑机理及调控其界面摩擦行为具有重要意义。本文基于微观实验，结合理论模型和原子模拟，在超高真空和宽温域条件下研究了a-C:H碳膜界面磨合的摩擦演化机理。 首先，基于超高真空变温原子力显微镜实现了a-C:H碳膜的微观超滑，并建立了摩擦化学诱导摩擦演化至超滑态的动力学模型。借助逐级加载往复扫描实验，揭示了微观磨合的双阶段摩擦演化规律：高摩擦的第一阶段源于碳膜表面氧化层的去除，氧化层去除速率与接触应力及温度之间的关系符合热激活-应力辅助Arrhenius模型；而第二阶段中的摩擦大幅下降至超滑态主要归因于界面结构的有序化转变，该阶段碳膜几乎无磨损发生，进一步基于描述相变形核-生长的Johnson-Mehl-Avrami-Kolmogorov理论建立了有序化转变诱导摩擦演化的动力学模型。 其次，在298-473 K高温范围内研究了不同含氢量a-C:H碳膜的微观摩擦演化规律。结果表明，低含氢a-C:H碳膜（10 at.%H）在高温范围内具有更优异的自润滑性能，且摩擦演化规律符合热激活的界面有序化转变机理；而高含氢a-C:H碳膜（40 at.%H）在高温下摩擦磨损增大，结合原子模拟揭示了碳膜表面类石墨片层机械化学剥落的高温磨损机理。 最后，在103-298 K低温范围内研究了以上两种含氢a-C:H碳膜的微观摩擦演化规律。结合高温实验，探索了有序化转变动力学模型在宽温域下的适用性，并发现低含氢a-C:H碳膜在173 K以下摩擦磨损增大，揭示了转移膜缺陷增多且结构无序化转变的低温磨损机理；而高含氢a-C:H碳膜可在低温下实现稳定的低摩擦态，但173 K以下存在非热效应，导致了有序化转变偏离热激活的Sub-Arrhenius规律，该规律符合量子隧穿修正的Arrhenius模型，并进一步结合原子模拟揭示了氢转移量子隧穿效应促进摩擦相变的碳膜低温超滑机制。 综上，本研究为发展适用于真空和宽温域等极端工况下的碳膜自润滑材料体系提供了实验方法和理论指导。

a-C:H as one kind of diamond-like carbon (DLC) film, is capable of achieving superlubricity at macroscale, having potential application prospects in extreme conditions such as vacuum and wide temperature range. However, different from two-dimensional materials, the running-in stage is an important prerequisite for achieving the superlubricity of a-C:H film, which involves a series of complex interfacial tribochemical reactions. Understanding the kinetics of tribochemical reactions during friction evolution process is of great significance for further exploring superlubricity mechanism of DLC film. In this work, combining with microscopic experiments, theoretical models and atomic simulations, we systematically study the friction evolution process and tribochemical mechanisms of a-C:H film under ultrahigh vacuum and wide temperature range. Firstly, superlubricity of a-C:H film at single-asperity contact level is achieved based on ultrahigh vacuum variable temperature atomic force microscope (UHV-VT-AFM), and the kinetic model of tribochemistry induced friction evolution towards superlubric state is established. By designing a stepwise loading-repeated running (SL-RR) experiments, we reveal the two-stage friction evolution law during microscopic running-in process: the first high friction stage is attributed to the removal of oxide layer on a-C:H surface, thus wear of carbon film and material transfer mainly occur in this stage. The relationship between removal rate and temperature or contact stress can be described quantitatively by a stress-activated Arrhenius model; In the second stage, a large friction decrease occurs due to a structural ordering transformation, and there is almost no wear on the sliding interface. Furthermore, based on the Johnson–Mehl–Avrami–Kolmogorov theory of solid phase transformation, a kinetic model to describe friction evolution induced by structural ordering transformation is established. Secondly, the friction evolution behavior of a-C:H film with different hydrogen content is studied in the high temperature range from 298 K to 473 K. More specifically, the a-C:H film with 10 at.%H exhibit lower friction and better interface stability in the high temperature range, and the friction evolution process is dominated by the thermally activated structural ordering mechanism; while the interfacial friction and wear increases with increasing of temperature for a-C:H film with 40 at.%H. Assisted by atomic simulation, the wear mechanism of temperature induced mechano-chemical exfoliation of graphitic layers was revealed. Finally, the friction evolution behavior of above two kind a-C:H film is studied in the low temperature range from 103 K to 298 K. Combined with the discussion in high temperature range, the applicability of the ordering transformation kinetic model in a wide temperature range is explored. We further found the friction and wear of a-C:H film with 10 at.%H increases at low temperature range below 173 K, which is due to the increased defects and disordered structures in the transfer film, as confirmed by microsphere experiments and Raman spectra characterization. For a-C:H film with 40 at.%H, the stable low friction interface can sustain at low temperature to 103 K. However, we observe an athermal effect below 173 K, which results in the deviation of ordering transformation kinetics from Arrhenius law to Sub-Arrhenius law. To describe this deviation phenomenon, we introduce a quantum tunneling modified Arrhenius model, and further reveal the hydrogen transfer induced quantum tunneling effect by atomic simulation. In conclusion, this study provides experimental methods and theoretical basis for the development DLC films applied in extreme conditions such as vacuum and wide temperature range.