不同基底石墨烯涂层的层间滑移减磨性能研究

石墨烯薄膜作为一种二维材料,是提高微/纳机电系统(MEMS/NEMS)摩擦力学性能的优异润滑剂.为了探究基底材料和石墨烯层数对其减磨性能的影响,本文通过在不同基底制备了不同层数的石墨烯涂层,利用原子力显微镜(AFM)实验和分子动力学(MD)仿真结合的方法,研究了石墨烯层数对减磨效应的影响.并且通过建立不同层数石墨烯涂层的摩擦性能分析模型,探究出石墨烯层间滑移是产生减磨的主要因素.结果表明:在不同载荷下,石墨烯涂层对硅基底和铜基底均有优异的减磨效果,摩擦力随着石墨烯层数的增加逐渐降低,当石墨烯层数大于10层时,达到最优99.3%的减磨效果.通过仿真分析发现,随着层数增加,石墨烯与基底的干摩擦转变为石墨烯的层间摩擦,并产生层间剪切滑移,石墨烯层间滑移是导致多层石墨烯优异减磨性能的主要因素.     

高通量计算二维材料界面摩擦

建立了基于第一性原理方法研究二维材料界面摩擦的高通量计算程序,该程序实现了自动化批量建模、批量提交任务、多任务并发计算,以及计算结果自动收集、处理和图像绘制,使用该程序可以节省时间.采用此程序计算了不同层间距离下双层氮化硼和双层石墨烯的滑移势能面,及层间界面摩擦力和摩擦系数.研究发现,随着层间距离减小,双层氮化硼界面的平均摩擦力近似线性增大,摩擦系数为0.11—0.17,双层石墨烯界面摩擦力先增大后减小再增大,其摩擦系数在12 nN载荷下达到最小值(0.014),这些结果与已有研究结果一致,验证了该计算程序的可靠性.此外还研究了表面氢化和氟化对双层氮化硼界面摩擦的影响,发现氟化氮化硼/氮化硼界面的摩擦系数更低.     

石墨烯层间纳米摩擦性质的第一性原理研究

基于密度泛函理论的第一性原理计算方法研究了纳米尺度下石墨烯层间摩擦现象, 探讨了对称和非对称两种情况下双层石墨烯层间沿不同方向的摩擦性质. 研究发现对于对称的双层石墨烯, 层间摩擦沿不同方向同性; 摩擦因数依赖于正压力, 随正压力增大, 摩擦因数的变化曲线分为三个阶段, 在较小以及较大压力下, 摩擦因数遵循Amonton法则不随压力变化而变化; 而在中间3-6 nN阶段, 摩擦因数随压力增加线性增加. 整个研究压力范围内摩擦因数在0.05-0.25之间. 对于非对称性双层石墨烯层间摩擦, 不同压力下摩擦因数在0.006上下波动, 摩擦因数较两层对称性石墨烯大大降低. 上述研究结果与实验一致.     

石墨烯在强激光作用下改性的拉曼研究

采用化学气相沉积法制备了不同层数的石墨烯样品.根据石墨烯透过率曲线分析石墨烯样品层数与550 nm处透过率关系的同时,利用拉曼光谱法分析了不同层数石墨烯样品在强激光辐照下的损伤特性.结果表明:单层石墨烯样品经强激光辐照后,G带和2D带均向高频移动;多层石墨烯样品经强激光辐照后只有G带发生了略微的频移;石墨烯样品拉曼光谱G带与2D带强度比值表征了石墨烯的层数,此比值随激光辐照时间的增加而减小,这表明强激光对石墨烯样品具有明显的剥离现象.     

1064nm纳秒激光对石墨烯的损伤效应研究

通过化学气相沉积法制备,并转移到基片得到1~3层石墨烯样品。利用霍尔效应及微区拉曼光谱测量,结合光学显微镜观察,分析了不同层数石墨烯在1064nm纳秒激光辐照下的损伤特性。实验发现1~3层石墨烯的激光损伤阈值依次降低,分别为:单层0.45J/cm2,2层0.34J/cm2,3层0.23J/cm2。激光强度超过阈值时,石墨烯薄膜电阻增大,载流子迁移率降低。通过光学显微镜观察发现局部区域破损,破损区域的拉曼光谱中1580cm-1左右的G峰和2700cm-1左右的2D峰高度比发生变化。实验结果表明1064nm纳秒激光辐照石墨烯主要为剥离作用。     

悬浮石墨烯摩擦特性

石墨烯作为固体润滑剂在微/纳米机电系统中具有巨大的应用潜力.本文在SiO_2/Si基底上制备了微孔阵列,将石墨烯剥离在微孔上,形成悬浮结构.使用原子力显微镜研究悬浮石墨烯和支撑石墨烯的摩擦特性,结果表明:悬浮石墨烯表面摩擦力比基底支撑石墨烯明显减小,同时在支撑石墨烯上出现的摩擦增强效应也消失.随着石墨烯厚度的增大,面外刚度逐渐增大,悬浮石墨烯与支撑石墨烯的摩擦力差异逐渐减小.此外,使用预磨损探针时,悬浮石墨烯和支撑石墨烯的摩擦力都显著增大,且悬浮石墨烯的摩擦力依然比支撑石墨烯小.通过对比不同厚度石墨烯,不同针尖半径时悬浮石墨烯与支撑石墨烯表面摩擦力的变化,揭示了面外变形对石墨烯摩擦力的影响,为有效提高石墨烯固体润滑剂的摩擦性能提供了理论指导.     

缺陷单层和双层石墨烯的拉曼光谱及其激发光能量色散关系

拉曼光谱作为一种无破坏性、快速且敏锐的测试技术已经成 为表征石墨烯样品和研究其缺陷的最重要的实验手段之一. 本论文用离子注入在单层和双层石墨烯中产生缺陷, 并利用拉曼光谱研究了存在缺陷时单层和双层石墨烯的一阶和二阶拉曼模, 单层石墨烯的D模为双峰结构, 而双层石墨烯的D模具有四峰结构. 同时, 利用四条激光线系统地研究了本征和缺陷单层和双层石墨烯的拉曼峰频率的激发光能量依赖关系, 并基于石墨材料的双共振拉曼散射机理指认了离子注入后样品各拉曼峰的物理根源. 关键词： 石墨烯 缺陷 拉曼光谱 能量色散关系     

铜基底上双层至多层石墨烯常压化学气相沉积法制备与机理探讨

化学气相沉积是目前最重要的ー种制备高质量、大面积石墨烯的方法.而铜是化学气相沉积法制备石墨烯中最常用的生长基底.虽然有大量文章报道了关于石墨烯的生长条件及生长机理,但是作为最广泛采用的材料,铜基底上双层及多层石墨烯的生长机理仍然在探索中,本文采用常压化学气相沉积法,以乙醇为碳源在铜基底上生长石墨烯,并将其转移到SiO_2/Si基底上.用场发射扫描电镜、透射电镜、拉曼光谱、光学显微镜对所制备的石墨烯进行表征和层数分析,对转移到不同基底上的不同层数的石墨烯进行了透光性分析.结果表明,常压条件下铜箔表面能够生长出质量较高、连续性较好的双层至多层石墨烯.此外,我们还对铜基底上双层至多层石墨烯的生长机理进行了探讨.     

退火温度调控多层折叠石墨烯力学性能的分子动力学模拟

退火是石墨烯宏观组装材料常用的制备工艺之一,广泛用于其性能的调控.在石墨烯基材料中,石墨烯片层由于其自身的二维特性通常在微纳米尺度下呈现出多层折叠的结构.然而这种微观结构对材料力学性能退火调控的影响仍未得到充分的了解.为了阐明多层折叠石墨烯力学性能与退火温度间的调控关系,基于分子动力学模拟研究了材料弹性模量、拉伸强度、极限应变以及断裂韧性等关键力学性能参数随退火温度的变化规律,进而结合观察微观结构的演化过程揭示了性能调控现象的物理机制.结果表明:更高的退火温度将增强多层折叠石墨烯的弹性模量与拉伸强度,但同时削弱了其极限应变,并且其断裂韧性能够在一定退火温度范围内实现强化.研究发现,以上力学性能的调控作用归因于更高的退火温度将造成更加密集的层间交联,从而增强了折叠区域层间界面的相互作用,并限制了折叠结构的形态展开,致使结构破坏模式发生转变.     

双层石墨烯的化学气相沉积法制备及其光电器件

石墨烯是一种具有优异性质,在光电及能源领域具有巨大应用前景的二维材料.尽管单层石墨烯具有超高的迁移率,但是它的能带结构具有狄拉克锥(K点),即价带和导带并未有明显分离,所以在半导体器件方面的应用受到一定的限制.由双层石墨烯搭建而成的双门器件,在施加外加电场的情况下,它的带隙可以打开,并在一定范围内可调,这种性质赋予了双层石墨烯在半导体器件应用方面的前景.然而机械或者液相剥离石墨烯,在层数和大小方面可控性较差.如何通过化学气相沉积法可控制备双层石墨烯是目前研究的核心问题之一.本文主要综述了如何通过化学气相沉积法制备双层石墨烯和制备双层石墨烯器件的一系列工作,其中包括最新的研究进展,对生长机理的研究做了详细的介绍和讨论,并对该领域的发展进行了展望.     

Tribological behavior of diamond-like carbon film with different tribo-pairs: A size effect study

A friction force microscope (FFM) with different probes and a ball-on-disk (BOD) tribo-meter were used to investigate the tribological properties of diamond-like carbon (DLC) films. DLC films were prepared by chemical vapor deposition (CVD) method by altering the deposition parameters, and their morphologies and structural information were examined with an atomic force microscope (AFM) and the Raman spectrum. The wear traces of the DLC films after frictional tests were analyzed by an optical microscope. It is found that surface roughness and adhesion play important roles in characterizing the tribological properties of DLC films using FFM. Moreover, the debris accumulation is another significant factor affecting the frictional behavior of DLC films, especially for the sharp tip. The difference in coefficients of friction (COFs) obtained by the BOD method among different DLC films under water lubrication is much smaller than the case without water lubrication. The variation trends in COF for the flat tip and the BOD test are similar in comparison with the result obtained with the sharp tip. The wear traces after frictional tests suggest that DLC films under water lubrication are prone to be damaged more readily.     

Casimir friction force between a SiO<Subscript>2</Subscript> probe and a graphene-coated SiO<Subscript>2</Subscript> substrate

The possibility of mechanical detection of Casimir friction with the use of a noncontact atomic force microscope is discussed. A SiO₂ probe tip located above a graphene-coated SiO₂ substrate is subjected to the frictional force caused by a fluctuating electromagnetic field produced by a current in graphene. This frictional force will create the bend of a cantilever, which can be measured by a modern noncontact atomic force microscope. Both the quantum and thermal contributions to the Casimir frictional force can be measured using this experimental setup. This result can also be used to mechanically detect Casimir friction in micro- and nanoelectromechanical systems.     

Superlubricity of graphite

Using a home-built frictional force microscope that is able to detect forces in three dimensions with a lateral force resolution down to 15 pN, we have studied the energy dissipation between a tungsten tip sliding over a graphite surface in dry contact. By measuring atomic-scale friction as a function of the rotational angle between two contacting bodies, we show that the origin of the ultralow friction of graphite lies in the incommensurability between rotated graphite layers, an effect proposed under the name of "superlubricity" [Phys. Rev. B 41, 11 837 (1990)]].     

基于滑动势能面的二维材料原子尺度摩擦行为的量化计算

近年来,二维材料优异的摩擦特性成为人们关注的焦点,然而目前缺乏理论上对其摩擦力进行快速、有效、精确的计算预测方法.本文提出采用密度泛函理论计算真实体系的滑动势能面,利用得到的"数值型势能面"替代传统的解析势函数,并结合Prandtl-Tomlinson模型,量化求解具有复杂形状势能面的真实二维材料体系的摩擦行为.基于该方法,揭示了原子力显微镜实验中观察到的石墨烯Moire纹超晶格结构的双周期"黏-滑"摩擦现象;理论预测了二维材料异质结构的层间超低摩擦现象,相对于同质材料,其静摩擦力和滑动摩擦力均成数量级降低,发现势能面起伏和驱动弹簧刚度均会影响层间相对滑动路径,进而对层间的摩擦行为产生影响.该方法同样可拓展到其他van der Waals作用主导的界面摩擦体系.     

Surface adhesion properties of graphene and graphene oxide studied by colloid-probe atomic force microscopy

Surface adhesion properties are important to various applications of graphene-based materials. Atomic force microscopy is powerful to study the adhesion properties of samples by measuring the forces on the colloidal sphere tip as it approaches and retracts from the surface. In this paper we have measured the adhesion force between the colloid probe and the surface of graphene (graphene oxide) nanosheet. The results revealed that the adhesion force on graphene and graphene oxide surface were 66.3 and 170.6 nN, respectively. It was found the adhesion force was mainly determined by the water meniscus, which was related to the surface contact angle of samples.     

Effects of a self-assembled monolayer on the sliding friction and adhesion of an Au surface

The friction and adhesion mechanisms with and without a self-assembled monolayer (SAM) in nanotribology were studied using molecular dynamics (MD) simulation. The MD model consisted of two gold planes with and without n-hexadecanethiol SAM chemisorbed to the substrate, respectively. The molecular trajectories, tilt angles, normal forces, and frictional forces of the SAM and gold molecules were evaluated during the frictional and relaxation processes for various parameters, including the number of CH₂ molecules, the interference magnitude, and whether or not the SAM lubricant was used. The various parameters are discussed with regard to frictional and adhesion forces, mechanisms, and molecular or atomic structural transitions. The stick–slip behavior of SAM chains can be completely attributed to the van der Waals forces of the chain/chain interaction. When the number of CH₂ molecules was increased, the SAM chains appeared to have bigger tilt angles at deformation. The magnitude of the strain energy that was saved and relaxed is proportional to the elastic deformable extent of the SAM molecules. The frictional force was higher for long chain molecules. With shorter SAM molecules, the adhesion force behavior was more stable during the compression and relaxation processes. A surface coated with a SAM can increase nano-device lifetimes by avoiding interface effects like friction and adhesion. PACS 52.65.Yy; 81.40.Pq; 81.16; 68.35.-p     

Effect of C60 molecular rotation on nanotribology

The effect of C60 molecular rotation on the nanotribological properties of C60 single crystal surfaces has been studied by atomic/frictional force microscopy. The orientational order-disorder phase transition, in which the high temperature C60 free rotation is reduced to a low temperature hindered rotation, is shown to give rise to an abrupt change in friction and adhesion. This change in frictional force is quantitatively consistent with the observed change in adhesion. The similar slopes of the friction versus load curves in both phases indicate that the friction coefficient in the two phases remains about the same. Hence the C60 rotation does not provide an additional energy dissipation channel in the friction process.     

Lateral force microscopy in low normal force limit

We have studied frictional force between SiN tip and Si surface by using lateral force microscopy. The cantilever we have used has very low stiffness of 0.006 N/m, and the normal force acting on the surface was much lower than the attractive force such as van der Waals force. In this low normal force limit, it was found that the frictional force did not depend on the normal force. We suggest a calibration method to estimate the attractive force from the lateral force data in this limit. The estimated attractive force between Si sample and SiN tip with radius of 10 nm was 0.4 nN in flat region and 0.65 nN at the corner of a rectangular hole.