Lin Jianliang, Park In-Wook, Mishra Brajendra, Pinkas Malki, Moore John J, Anton Jennifer M, Kim Kwang Ho, Voevodin Andrey A, Levashov Evgeny A
Advanced Coatings and Surface Engineering Laboratory (ACSEL), Colorado School of Mines, Golden, CO 80401, USA.
J Nanosci Nanotechnol. 2009 Jul;9(7):4073-84. doi: 10.1166/jnn.2009.m13.
Nanostructured, nanocomposite binary (TiC-a:C), ternary (Cr-Al-N), quaternary (Ti-B-C-N) and quinternary (Ti-Si-B-C-N) multicomponent films have been deposited using unbalanced magnetron sputtering (UBMS) and closed field unbalanced magnetron sputtering (CFUBMS) from both elemental and composite targets. Approaches to control the film chemistry, volume fraction and size of the multicomponent species, and pulsed ion energy (ion flux) bombardment to tailor the structure and properties of the films for specific tribological applications, e.g., low friction coefficient and low wear rate, are emphasized. The synthesized films are characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), nanoindentation, and microtribometry. The relationships between processing parameters (pulsed ion energy and ion flux), thin film microstructure, mechanical and tribological properties are being investigated in terms of the nanocrystalline-nanocrystalline and nanocrystalline-amorphous composite thin film systems that are generated. In the Ti-Si-B-C-N films, nanocomposites of solid solutions, e.g., nanosized (Ti,C,N)B2 and Ti(C,N) crystallites are embedded in an amorphous TiSi2 and SiC matrix including some carbon, SiB4, BN, CN(x), TiO2 and B2O3 components. The Ti-Si-B-C-N coating with up to 150 W Si target power exhibited a hardness of about 35 GPa, a high H/E ratio of 0.095, and a low wear rate of from approximately 3 to approximately 10 x 10(-6) mm3/(Nm). In another aspect, using increased ion energy and ion flux, which are generated by pulsing the power of the target(s) in a closed field arrangement, to provide improved ion bombardment on tailoring the structure and properties of TiC-a:C and Cr-Al-N coatings are demonstrated. It was found that highly energetic species (up to hundreds eV) were found in the plasma by pulsing the power of the target(s) during magnetron sputtering. Applying higher pulse frequency and longer reverse time (lower duty cycle) will result in higher ion energy and ion flux in the plasma, which can be utilized to improve the film structure and properties. For example, optimum properties of the TiC-a:C coating were a hardness of 35 to 40 GPa and a COF of 0.2 to 0.22 for moderate maximum ion energies of 70 to 100 eV, and a super high hardness of 41 GPa and low wear rate of 3.41 x 10(-6) mm3N(-1) m(-1) was obtained for Cr-Al-N coatings deposited with a maximum ion energy of 122 eV. These conditions can be achieved by adjusting the pulsing parameters and target voltages. However, the pulsed ion energy together with the applied substrate bias are need to be carefully controlled in order to avoid excessive ion bombardment (e.g., the maximum ion energy is larger than 180 eV in the current study), which will responsible for an increase in point and line defects, and high residual stress in the crystalline structure.
采用非平衡磁控溅射(UBMS)和闭场非平衡磁控溅射(CFUBMS)技术,通过元素靶材和复合靶材沉积了纳米结构的纳米复合二元(TiC-a:C)、三元(Cr-Al-N)、四元(Ti-B-C-N)和五元(Ti-Si-B-C-N)多组分薄膜。重点介绍了控制薄膜化学组成、多组分物质的体积分数和尺寸的方法,以及采用脉冲离子能量(离子通量)轰击来调整薄膜结构和性能以满足特定摩擦学应用(如低摩擦系数和低磨损率)的方法。使用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)、纳米压痕和微摩擦学对合成薄膜进行了表征。针对生成的纳米晶-纳米晶和纳米晶-非晶复合薄膜体系,研究了工艺参数(脉冲离子能量和离子通量)、薄膜微观结构、力学性能和摩擦学性能之间的关系。在Ti-Si-B-C-N薄膜中,固溶体纳米复合材料,如纳米尺寸的(Ti,C,N)B2和Ti(C,N)微晶,嵌入在包含一些碳、SiB4、BN、CN(x)、TiO2和B2O3组分的非晶TiSi2和SiC基体中。在Si靶功率高达150W的情况下制备的Ti-Si-B-C-N涂层,硬度约为35GPa,H/E比高达0.095,磨损率低,约为3至10×10(-6)mm3/(Nm)。另一方面,展示了通过在闭场配置中对靶材功率进行脉冲调制来增加离子能量和离子通量,从而在调整TiC-a:C和Cr-Al-N涂层的结构和性能时提供更好的离子轰击效果。研究发现,在磁控溅射过程中通过对靶材功率进行脉冲调制,等离子体中会出现高能粒子(高达数百电子伏特)。施加更高的脉冲频率和更长的反向时间(更低的占空比)会导致等离子体中离子能量和离子通量增加,可用于改善薄膜结构和性能。例如,对于TiC-a:C涂层,在中等最大离子能量为70至100eV时,最佳性能为硬度35至40GPa,摩擦系数0.2至0.22;对于最大离子能量为122eV沉积的Cr-Al-N涂层,获得了41GPa的超高硬度和3.41×10(-6)mm3N(-1)m(-1)的低磨损率。这些条件可通过调整脉冲参数和靶电压来实现。然而,为避免过度离子轰击(如在本研究中最大离子能量大于180eV),需要仔细控制脉冲离子能量和施加的衬底偏压,过度离子轰击会导致点缺陷和线缺陷增加以及晶体结构中产生高残余应力。