By utilizing the reduced contact area of nanowires, we show that epitaxial growth of a broad range of semiconductors on graphene can in principle be achieved. A generic atomic model is presented which describes the epitaxial growth configurations applicable to all conventional semiconductor materials. The model is experimentally verified by demonstrating the growth of vertically aligned GaAs nanowires on graphite and few-layer graphene by the self-catalyzed vapor-liquid-solid technique using molecular beam epitaxy. A two-temperature growth strategy was used to increase the nanowire density. Due to the self-catalyzed growth technique used, the nanowires were found to have a regular hexagonal cross-sectional shape, and are uniform in length and diameter. Electron microscopy studies reveal an epitaxial relationship of the grown nanowires with the underlying graphitic substrates. Two relative orientations of the nanowire side-facets were observed, which is well explained by the proposed atomic model. A prototype of a single GaAs nanowire photodetector demonstrates a high-quality material. With GaAs being a model system, as well as a very useful material for various optoelectronic applications, we anticipate this particular GaAs nanowire/graphene hybrid to be promising for flexible and low-cost solar cells.

Ternary semiconductor nanowire arrays enable scalable fabrication of nano-optoelectronic devices with tunable bandgap. However, the lack of insight into the effects of the incorporation of Vy element results in lack of control on the growth of ternary III-V(1-y)Vy nanowires and hinders the development of high-performance nanowire devices based on such ternaries. Here, we report on the origins of Sb-induced effects affecting the morphology and crystal structure of self-catalyzed GaAsSb nanowire arrays. The nanowire growth by molecular beam epitaxy is changed both kinetically and thermodynamically by the introduction of Sb. An anomalous decrease of the axial growth rate with increased Sb2 flux is found to be due to both the indirect kinetic influence via the Ga adatom diffusion induced catalyst geometry evolution and the direct composition modulation. From the fundamental growth analyses and the crystal phase evolution mechanism proposed in this Letter, the phase transition/stability in catalyst-assisted ternary III-V-V nanowire growth can be well explained. Wavelength tunability with good homogeneity of the optical emission from the self-catalyzed GaAsSb nanowire arrays with high crystal phase purity is demonstrated by only adjusting the Sb2 flux.

We have demonstrated the growth of a unique wurtzite (WZ) GaAs nanowire (NW) with a zinc blende (ZB) GaAsSb insert by Au-assisted molecular beam epitaxy. An abrupt interface from the WZ GaAs phase to the ZB GaAsSb phase was observed, whereas an intermediate segment of a 4H polytype GaAs phase was found directly above the ZB GaAsSb insert. A possible mechanism for the different phase transitions is discussed. Furthermore, low temperature microphotoluminescence (micro-PL) measurements showed evidence of quantum confinement of holes in the GaAsSb insert.

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This thesis deals with the growth of GaAs nanowires (NWs) by molecular beam epitaxy (MBE) using vapor-liquid-solid method on various substrates including GaAs(111)B, Si(111) and graphene. The growth of the NWs on GaAs substrates was carried out by Au-catalyzed technique, whereas the growths on Si and graphene substrates were carried out using self-catalyzed technique that has been the main focus of this thesis. The long-term goal of this work was to produce p-n radial junction GaAs NWs for solar cell applications.Necessary conditions were established for obtaining vertical self-catalyzed GaAs NWs on Si(111), which is reproducible from run-to-run. One of the major issues in these NWs grown by both Au-and self-catalyzed techniques is their crystal structure. The Au-catalyzed GaAs NWs usually adopt a wurtzite (WZ) crystal phase, whereas the self-catalyzed NWs a zinc blende (ZB) phase. However, in both the cases the NWs contain stacking faults, rotational twins or/and a mixed crystal phase. The ZB and WZ phases show different optical properties, and one phase might be favored over other for certain applications. Therefore the crystal phase was controlled within single NWs by tuning the V/III ratio and introducing GaAsSb inserts. The change of the crystal phases was correlated with the change in the contact angle of the Ga droplet.Since the discovery of graphene, an ultra-thin two-dimensional material, the research on graphene has become an active field in recent years due to its remarkable properties including excellent electrical and thermal conductivities, mechanical strength and flexibility, and optical transparency. By growing the semiconductor NWs on graphene, a completely new hybrid system can be envisioned where the unique properties of both NWs and graphene can be utilized. Therefore we established a method for the growth of semiconductor NWs on graphene by demonstrating epitaxial growth of vertical GaAs and InAs NWs on different graphitic substrates.Core-shell heterostructure, doping, optical properties, and position controlled growth of self-catalyzed GaAs NWs were investigated. Growth of GaAs/GaAsSb coreshell NWs where the Sb content was tuned from about 10% -70% was studied. The effect of growth temperature and the Sb flux on the morphology of GaAsSb shell was investigated. In addition, by utilizing the core-shell geometry where the shell copies the crystal phase of the core, WZ phase of GaAsSb was demonstrated. Successful p-type doping of GaAs core using Be as dopant, and n-type doping of GaAs shell using Si and Te as dopants were achieved. To investigate the optical properties, GaAs/AlGaAs coreshell NWs were grown with different V/III ratios during the core growth. The NWs grown with high V/III ratio, despite containing a higher density of twinned ZB and WZ GaAs with SFs, were found to have superior optical quality as compared to the NWs grown with low V/III ratio that contain pure ZB GaAs. The observed V/III ratio dependent optical quality was correlated to the intrinsic defects such as As vac...

Many efficient light-emitting devices and photodetectors are based on semiconductors with, respectively, a direct or indirect bandgap configuration. The less known pseudodirect bandgap configuration can be found in wurtzite (WZ) semiconductors: here electron and hole wave-functions overlap strongly but optical transitions between these states are impaired by symmetry. Switching between bandgap configurations would enable novel photonic applications but large anisotropic strain is normally needed to induce such band structure transitions. Here we show that the luminescence of WZ GaAs nanowires can be switched on and off, by inducing a reversible direct-to-pseudodirect band structure transition, under the influence of a small uniaxial stress. For the first time, we clarify the band structure of WZ GaAs, providing a conclusive picture of the energy and symmetry of the electronic states. We envisage a new generation of devices that can simultaneously serve as efficient light emitters and photodetectors by leveraging the strain degree of freedom.

The optical properties of the wurtzite (WZ) GaAs crystal phase found in nanowires (NWs) are a highly controversial topic. Here, we study high-quality pure WZ GaAs/AlGaAs core-shell NWs grown by Au-assisted molecular beam epitaxy (MBE) with microphotoluminescence spectroscopy (μ-PL) and (scanning) transmission electron microscopy on the very same single wire. We determine the room temperature (294 K) WZ GaAs bandgap to be 1.444 eV, which is ∼20 meV larger than in zinc blende (ZB) GaAs, and show that the free exciton emission at 15 K is at 1.516 eV. On the basis of time- and temperature-resolved μ-PL results, we propose a Γ(8) conduction band symmetry in WZ GaAs. We suggest a method for quantifying the optical quality of NWs, taking into consideration the difference between the room and low temperature integrated PL intensity, and demonstrate that Au-assisted GaAs/AlGaAs core-shell NWs can have high PL brightness up to room temperature.

Device configurations that enable a unidirectional propagation of carriers in a semiconductor are fundamental components for electronic and optoelectronic applications. To realize such devices, however, it is generally required to have complex processes to make p-n or Schottky junctions. Here we report on a unidirectional propagation effect due to a self-induced compositional variation in GaAsSb nanowires (NWs). The individual GaAsSb NWs exhibit a highly reproducible rectifying behavior, where the rectifying direction is determined by the NW growth direction. Combining the results from confocal micro-Raman spectroscopy, electron microscopy, and electrical measurements, the origin of the rectifying behavior is found to be associated with a self-induced variation of the Sb and the carrier concentrations in the NW. To demonstrate the usefulness of these GaAsSb NWs for device applications, NW-based photodetectors and logic circuits have been made.