Controlling the crystallographic phase purity of III-V nanowires is notoriously difficult, yet this is essential for future nanowire devices. Reported methods for controlling nanowire phase require dopant addition, or a restricted choice of nanowire diameter, and only rarely yield a pure phase. Here we demonstrate that phase-perfect nanowires, of arbitrary diameter, can be achieved simply by tailoring basic growth parameters: temperature and V/III ratio. Phase purity is achieved without sacrificing important specifications of diameter and dopant levels. Pure zinc blende nanowires, free of twin defects, were achieved using a low growth temperature coupled with a high V/III ratio. Conversely, a high growth temperature coupled with a low V/III ratio produced pure wurtzite nanowires free of stacking faults. We present a comprehensive nucleation model to explain the formation of these markedly different crystal phases under these growth conditions. Critical to achieving phase purity are changes in surface energy of the nanowire side facets, which in turn are controlled by the basic growth parameters of temperature and V/III ratio. This ability to tune crystal structure between twin-free zinc blende and stacking-fault-free wurtzite not only will enhance the performance of nanowire devices but also opens new possibilities for engineering nanowire devices, without restrictions on nanowire diameters or doping.

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.

We have used transient terahertz photoconductivity measurements to assess the efficacy of two-temperature growth and core-shell encapsulation techniques on the electronic properties of GaAs nanowires. We demonstrate that two-temperature growth of the GaAs core leads to an almost doubling in charge-carrier mobility and a tripling of carrier lifetime. In addition, overcoating the GaAs core with a larger-bandgap material is shown to reduce the density of surface traps by 82%, thereby enhancing the charge conductivity.Semiconductor nanowires are promising new materials for implementation in nanoscale electronic and optoelectronic devices. Of particular interest are III-V semiconductor nanowires, which can exhibit a direct bandgap and a high electron mobility.1 However, the large surface-to-volume ratio inherent to nanowires results in the presence of surface traps offering easy access to carrier and exciton recombination pathways.2,3 In addition, one-temperature growth techniques have been shown to cause a significant twin-defect (stacking-defect) density within the nanowires. 4 Refinements in the epitaxial growth of these nanowires are therefore essential in order for their optoelectronic and crystallographic standards to approach those of bulk material.2,6,7 Such efforts are complicated by the fact that electrical measurements conducted on nanowires to determine charge-carrier mobility are often obscured by properties of the electrical contacts. Most contactless spectroscopic probes of nanowires to date have relied upon low-temperature photoluminescence measurements to characterize optoelectronic quality by measuring excitonic dynamics and radiative quantum efficiency. 2,6However, for use of these materials in nanoelectronics and optoelectronics, it is essential to determine charge-carrier mobility and lifetime at room temperature.In this study, we have conducted transient photoconductivity measurements on an ensemble of nanowires in order to assess the effect of nearly defect-free (two-temperature) growth and core-shell encapsulation technologies on charge-carrier trapping and mobility. Optical-pump terahertz-probe spectroscopy was employed as a noncontact ultrafast probe of the room-temperature photoconductivity with subpicosecond resolution. We demonstrate that both two-temperature growth and encapsulation of the GaAs nanowires with a higher band gap material lead to significant increases in the lifetime of free charge carriers. Encapsulation of the nanowires is shown to be highly effective, reducing the areal density of surface traps to one-seventh of that for the untreated wires. Importantly, we find that moving from one-temperature growth to a two-temperature procedure (comprising a brief high-temperature step for nucleation and a longer lower-temperature phase for prolonged growth 4 ) increases the intrinsic carrier mobility of the wires from 1200 cm 2 /(V s) to 2250 cm 2 /(V s).All nanowire samples were initially grown onto a GaAs substrate as shown in a representative scanning electron microscopy ...