Hiroshi Anzai

True Vapor–Liquid–Solid Process Suppresses Unintentional Carrier Doping of Single Crystalline Metal Oxide Nanowires

Single crystalline nanowires composed of semiconducting metal oxides formed via a vapor-liquid-solid (VLS) process exhibit an electrical conductivity even without an intentional carrier doping, although these stoichiometric metal oxides are ideally insulators. Suppressing this unintentional doping effect has been a challenging issue not only for metal oxide nanowires but also for various nanostructured metal oxides toward their semiconductor applications. Here we demonstrate that a pure VLS crystal growth, which occurs only at liquid-solid (LS) interface, substantially suppresses an unintentional doping of single crystalline SnO2 nanowires. By strictly tailoring the crystal growth interface of VLS process, we found the gigantic difference of electrical conduction (up to 7 orders of magnitude) between nanowires formed only at LS interface and those formed at both LS and vapor-solid (VS) interfaces. On the basis of investigations with spatially resolved single nanowire electrical measurements, plane-view electron energy-loss spectroscopy, and molecular dynamics simulations, we reveal the gigantic suppression of unintentional carrier doping only for the crystal grown at LS interface due to the higher annealing effect at LS interface compared with that grown at VS interface. These implications will be a foundation to design the semiconducting properties of various nanostructured metal oxides.

Tailoring Nucleation at Two Interfaces Enables Single Crystalline NiO Nanowires via Vapor-Liquid-Solid Route.

Here we show a rational strategy to fabricate single crystalline NiO nanowires via a vapor-liquid-solid (VLS) route, which essentially allows us to tailor the diameter and the spatial position. Our strategy is based on the suppression of the nucleation at vapor-solid (VS) interface, which promotes nucleation only at the liquid-solid (LS) interface. Manipulating both the supplied material fluxes (oxygen and metal) and the growth temperature enables enhancement of the nucleation only at the LS interface. Furthermore, this strategy allows us to reduce the growth temperature of single crystalline NiO nanowires down to 550 °C, which is the lowest growth temperature so far reported.