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 SnO 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.

Here, we show the effect of water–organic (acetone, tert -butyl alcohol, and isopropanol) cosolvents on nucleation and anisotropic crystal growth of solution-synthesized ZnO nanowires. The addition of organic solution does not alter the face-selective crystal growth nature but significantly promotes the crystal growth of both length and diameter of the nanowires. Systematic investigations reveal that a variation of the relative dielectric constant in the cosolvent can rigorously explain the observed effect of the water–organic cosolvent on the ZnO nanowire growth via the degree of supersaturation for the nucleation. The difference between acetone, tert -butyl alcohol, and isopropanol on the cosolvent effect can be interpreted in terms of a local solvent-sorting effect.

In general, the electrical conductivities of n-type semiconducting metal oxide nanostructures increase with the decrease in the oxygen partial pressure during crystal growth owing to the increased number of crystal imperfections including oxygen vacancies. In this paper, we report an unusual oxygen partial pressure dependence of the electrical conductivity of single-crystalline SnO 2 nanowires grown by a vapor−liquid−solid (VLS) process. The electrical conductivity of a single SnO 2 nanowire, measured using the four-probe method, substantially decreases by 2 orders of magnitude when the oxygen partial pressure for the crystal growth is reduced from 10 −3 to 10 −4 Pa. This contradicts the conventional trend of n-type SnO 2 semiconductors. Spatially resolved single-nanowire electrical transport measurements, microstructure analysis, plane-view electron energy-loss spectroscopy, and molecular dynamics simulations reveal that the observed unusual oxygen partial pressure dependence of the electrical transport is attributed to the intrinsic differences between the two crystal growth interfaces (LS and VS interfaces) in the critical nucleation of the crystal growth and impurity incorporation probability as a function of the oxygen partial pressure. The impurity incorporation probability at the LS interface is always lower than that at the VS interface, even under reduced oxygen partial pressures.

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.