Department of Chemistry, University of Kentucky , Lexington, Kentucky 40506, United States.
ACS Nano. 2014 Jun 24;8(6):5441-8. doi: 10.1021/nn5007804. Epub 2014 May 16.
The well-known vapor-liquid-solid (VLS) mechanism results in high-purity, single-crystalline wires with few defects and controllable diameters, and is the method of choice for the growth of nanowires for a vast array of nanoelectronic devices. It is of utmost importance, therefore, to understand how such wires interact with metallic interconnects-an understanding which relies on comprehensive knowledge of the initial growth process, in which a crystalline wire is ejected from a metallic particle. Though ubiquitous, even in the case of single elemental nanowires the VLS mechanism is complicated by competing processes at multiple heterogeneous interfaces, and despite decades of study, there are still aspects of the mechanism which are not well understood. Recent breakthroughs in studying the mechanism and kinetics of VLS growth have been strongly aided by the use of in situ techniques, and would have been impossible through other means. As well as several systematic studies of nanowire growth, reports which focus on the role and the nature of the catalyst tip reveal that the stability of the droplet is a crucial factor in determining nanowire morphology and crystallinity. Additionally, a reverse of the VLS process dubbed solid-liquid-vapor (SLV) has been found to result in the formation of cavities, or "negative nanowires". Here, we present a series of heating studies conducted in situ in the transmission electron microscope (TEM), in which we observe the complete dissolution of metal oxide nanowires into the metal catalyst particles at their tips. We are able to consistently explain our observations using a solid-liquid-vapor (SLV) type mechanism in which both evaporation at the liquid-vapor interface and adhesion of the catalyst droplet to the substrate surface contribute to the overall rate.
众所周知,气-液-固(VLS)机制能够生成高纯、单晶、缺陷少且直径可控的线材,是用于生长各种纳米电子器件用纳米线的首选方法。因此,了解这些线材与金属互连体的相互作用至关重要——这种理解依赖于对初始生长过程的全面了解,在这个过程中,晶须从金属颗粒中被喷出。尽管 VLS 机制在多个异质界面上存在多种竞争过程,即使在单元素纳米线的情况下也是如此,但经过几十年的研究,仍有一些机制方面的问题尚未得到很好的理解。通过使用原位技术,最近在 VLS 生长的机制和动力学研究方面取得了突破,如果没有这些技术,这些突破是不可能实现的。除了对纳米线生长进行了多项系统研究外,还有一些重点关注催化剂尖端作用和性质的报告表明,液滴的稳定性是决定纳米线形态和结晶度的关键因素。此外,还发现一种被称为固-液-汽(SLV)的 VLS 过程的逆转会导致空腔或“负纳米线”的形成。在这里,我们展示了一系列在透射电子显微镜(TEM)中进行的原位加热研究,在这些研究中,我们观察到金属氧化物纳米线完全溶解在其尖端的金属催化剂颗粒中。我们能够使用固-液-汽(SLV)型机制一致地解释我们的观察结果,该机制认为,在液-汽界面处的蒸发和催化剂液滴与基底表面的粘附都对整体速率有贡献。