Halpern Jeffrey M, Martin Heidi B
Department of Chemical Engineering, Case Western Reserve University, Cleveland, OH 44106, USA.
Diam Relat Mater. 2014 Feb 1;42:33-40. doi: 10.1016/j.diamond.2013.11.010.
Molybdenum-rhenium (Mo/Re) and tungsten-rhenium (W/Re) alloys were investigated as substrates for thin-film, polycrystalline boron-doped diamond electrodes. Traditional, carbide-forming metal substrates adhere strongly to diamond but lose their ductility during exposure to the high-temperature (1000°C) diamond, chemical vapor deposition environment. Boron-doped semi-metallic diamond was selectively deposited for up to 20 hours on one end of Mo/Re (47.5/52.5 wt.%) and W/Re (75/25 wt.%) alloy wires. Conformal diamond films on the alloys displayed grain sizes and Raman signatures similar to films grown on tungsten; in all cases, the morphology and Raman spectra were consistent with well-faceted, microcrystalline diamond with minimal sp carbon content. Cyclic voltammograms of dopamine in phosphate-buffered saline (PBS) showed the wide window and low baseline current of high-quality diamond electrodes. In addition, the films showed consistently well-defined, dopamine electrochemical redox activity. The Mo/Re substrate regions that were uncoated but still exposed to the diamond-growth environment remained substantially more flexible than tungsten in a bend-to-fracture rotation test, bending to the test maximum of 90° and not fracturing. The W/Re substrates fractured after a 27° bend, and the tungsten fractured after a 21° bend. Brittle, transgranular cleavage fracture surfaces were observed for tungsten and W/Re. A tension-induced fracture of the Mo/Re after the prior bend test showed a dimple fracture with a visible ductile core. Overall, the Mo/Re and W/Re alloys were suitable substrates for diamond growth. The Mo/Re alloy remained significantly more ductile than traditional tungsten substrates after diamond growth, and thus may be an attractive metal substrate for more ductile, thin-film diamond electrodes.
钼铼(Mo/Re)和钨铼(W/Re)合金被作为薄膜多晶掺硼金刚石电极的基底进行了研究。传统的形成碳化物的金属基底与金刚石紧密结合,但在暴露于高温(1000°C)的金刚石化学气相沉积环境中时会失去延展性。在Mo/Re(47.5/52.5重量%)和W/Re(75/25重量%)合金丝的一端选择性沉积掺硼半金属金刚石长达20小时。合金上的保形金刚石膜显示出与在钨上生长的膜相似的晶粒尺寸和拉曼特征;在所有情况下,形态和拉曼光谱都与具有最小sp碳含量的多面微晶金刚石一致。多巴胺在磷酸盐缓冲盐水(PBS)中的循环伏安图显示了高质量金刚石电极的宽窗口和低基线电流。此外,这些膜始终显示出明确的多巴胺电化学氧化还原活性。在弯曲至断裂旋转试验中,未涂层但仍暴露于金刚石生长环境的Mo/Re基底区域比钨更具柔韧性,可弯曲至试验最大值90°而不破裂。W/Re基底在弯曲27°后破裂,钨在弯曲21°后破裂。观察到钨和W/Re的脆性穿晶解理断裂表面。先前弯曲试验后Mo/Re的拉伸诱导断裂显示出具有可见韧性核心的韧窝断裂。总体而言,Mo/Re和W/Re合金是适合金刚石生长的基底。金刚石生长后,Mo/Re合金仍比传统钨基底具有显著更高的延展性,因此可能是用于更具延展性的薄膜金刚石电极的有吸引力的金属基底。