Paul Stuart Wilson

Mo2C nanowires and nanoribbons on Si by two-step vapor-phase growth

Transition-metal carbides in bulk form have historically been of technological interest primarily due to their excellent mechanical and refractory properties. As electronic materials these ceramic compounds are also particularly intriguing in that their electrical resistivity is relatively low compared to other ceramics and shows metallic temperature-dependent behavior. Some compositions also have superconducting transitions temperatures above 10°K. However, the synthesis of such materials in the form of one-dimensional nanostructures, which may be of interest for various nanoelectronic applications, is relatively difficult due to their refractory nature (Tmelt⩾2000°C). Here we report the synthesis of well-defined Mo2C nanowires and ribbons using a two-step approach in which we catalytically grow metal oxide nanostructures followed by in situ carburization. The growth mechanisms, microstructure, and initial electrical property measurements are discussed.

Mo2C Nanowires and Ribbons on Si via Two-Step Vapor Phase Growth

Transition metal carbides are an interesting class of electronic materials owing to their high electrical conductivity at room temperature, which is only slightly lower than that of their constituent transition metal elements. For example, the room temperature electrical resistivity of bulk Mo2 C is ∼70 μΩ-cm compared to that of Mo (4.85 μΩ-cm), whereas that of NbC is ∼50 μΩ-cm as compared to 15.2 μΩ-cm for Nb. Indeed, the temperature dependent resistivity of many transition metal carbides suggests metallic-like conduction. Furthermore, certain transition metal carbides are known to become superconducting, with transition temperatures ranging from 1.15 °K for TiC1−x to 14 °K for NbC. [1] They are also able to withstand high temperatures and are chemically stable. Initial synthesis of metal carbide nanorods was demonstrated using the carbon nanotube (CNT) confined reaction mechanism by Lieber and co-workers [2] and subsequent superconducting behavior was shown by Fukunaga et al. [3]. Vapor-liquid-solid growth was employed by Johnson et al. [4] to synthesize micron-sized carbide whiskers. Here, we have successfully synthesized Mo2 C nanorods and ribbons on Si substrates using a novel two-step catalytic approach, which allows for synthesis of such high temperature nanostructures at manufacturable temperatures (≤ 1000 °C) and time scales (≤ 60 min). In the first step we utilize a catalytic vapor phase process to grow Mo and/or molybdenum oxide nanostructures, which are subsequently carburized in situ to form the desired Mo2 C nanostructures. Unlike true VLS growth of carbides, in which high temperature (≤ 1100–1200 °C) is required to adequately dissolve carbon into the catalyst particles, our strategy is to react the nanostructures along their entire length with a carbon vapor source after creating the oxide/metal nanostructures, which for Mo2 C can be achieved at relatively low temperatures. (≤ 1000 °C). The nanorods and ribbons are polycrystalline, with a mean grain size of 20–50 nm and 50–150 nm, respectively. We hypothesize that the growth mechanism is a complex mixture of VLS, VSS, and auto-catalytic growth, in which molten catalyst nanoparticles enter a three phase region once the metal precursor is supplied. The growth then presumably continues via a vapor-solid-solid process and is possible assisted by the presence of various molybdenum oxide species on the surface. Initial single nanowire electrical measurements yield a higher resistivity than in the bulk, which is attributed to the fine grain sizes and/or the presence of an oxide layer. A discussion of the growth mechanism will be presented along with issues relating to single nanowire device fabrication and control of nanowire orientation.Copyright