Crystalline germanium (Ge) micro- and nanowires have been grown from aqueous electrolytes through an electrochemical liquid-liquid-solid (ec-LLS) process using eutectic bismuth indium (e-BiIn) alloy as the liquid metal electrode. This alloy represents the first non-Hg or non-Ga containing liquid metal to be used for the growth of a group IV semiconductor crystal below the boiling point of water. The electrochemical stability of e-BiIn in aqueous electrolyte was assessed through cyclic voltammetry, which showed the metal alloy was destabilized either by anodic oxidation at potentials more positive than −1.0 V vs E(Ag/AgCl) or by cathodic reduction of Bi to BiH₃ at potentials more negative than −1.4 V vs E(Ag/AgCl). Within this potential window, ec-LLS produced Ge micro- and nanowires that were evaluated with scanning electron microscopy, high resolution transmission electron microscopy, and selected area electron diffraction. The cumulative analyses showed pronounced crystallinity in the as-prepared Ge microwires and nanowires, with nanowires showing an unexpected coiled morphology. Atom probe tomography data showed some incorporation of In and Bi at 6 and 3 at. %, respectively. The tomography data further demonstrated that the distribution of the metals was not uniform, as In-rich clusters were observed. A high doping character in the as-prepared Ge nanowires was separately confirmed with two-terminal resistivity measurements. In total, this work not only identifies a new liquid metal type that is amenable for ec-LLS but also suggests strongly that the composition of the liquid metal influences the resultant crystal size, shape, and purity.

中文翻译：

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共晶-铋铟作为锗微丝和螺旋纳米线电化学液-液-固沉积的生长溶剂

晶体锗（Ge）微型和纳米线已经通过使用共晶铋铟（e-BiIn）合金作为液态金属电极的电化学液-液-固（ec-LLS）工艺从水性电解质中生长出来。该合金表示用于在水的沸点以下生长IV族半导体晶体的第一非Hg或非Ga的液态金属。通过循环伏安法评估了e-BiIn在水性电解质中的电化学稳定性，结果表明，金属合金在高于-1.0 V vs E（Ag / AgCl）的电势下通过阳极氧化或通过将Bi阴极还原为BiH来使金属合金不稳定。₃在电位比-1.4 V vs E更负的情况下（Ag / AgCl）。在此潜在窗口内，ec-LLS产生了Ge微米和纳米线，并通过扫描电子显微镜，高分辨率透射电子显微镜和选定区域电子衍射对其进行了评估。累积分析显示，所制备的Ge微线和纳米线具有明显的结晶度，而纳米线则显示出意外的卷曲形态。原子探针层析成像数据显示In和Bi在6和3 at处有一定结合。％， 分别。断层扫描数据进一步表明，由于观察到富In团簇，金属的分布不均匀。通过两端电阻率测量分别确认了所制备的Ge纳米线中的高掺杂特性。总共，