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.

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...

The performance of GaAs nanowire (NW) devices depends critically on the presence of crystallographic defects in the NWs such as twinning planes and stacking faults, and considerable effort has been devoted to understanding and preventing the occurrence of these. For self-catalysed GaAs NWs grown by molecular beam epitaxy (MBE) in particular, there are in addition other types of defects that may be just as important for NW-based optoelectronic devices. These are the point defects such as the As vacancy and the Ga antisite occurring due to the inherently Ga-rich conditions of the self-catalysed growth. Here we demonstrate experimentally the effects of these point defects on the optical properties of GaAs/AlGaAs core-shell NWs grown by self-catalysed MBE. The present results enable insight into the role of the point defects both on their own and in conjunction with crystallographic planar defects.

The growth of monocrystalline semiconductor nanowires on arbitrary substrates via the metal-induced crystallization (MIC) process extends the possible combinations of substrates and epitaxial active materials. However, it is still difficult to accomplish high-density vertical nanowire growth on the MIC polycrystalline Si(111) substrate. Here, the authors report on the growth of self-catalyzed GaAs nanowires by molecular beam epitaxy on MIC polycrystalline Si(111) substrates with different surface oxide conditions. Forming the surface oxide by annealing the freshly hydrofluoric acid-etched MIC polycrystalline Si(111) substrate in an ambient atmosphere is found to be a key step to grow high-density GaAs nanowires. Moreover, the addition of Sb during nanowire growth improves the density of vertical nanowires. Photoluminescence measurements reveal a high optical quality of the GaAs nanowires, indicating that the nanowires grown on MIC polycrystalline Si(111) substrate may be used as building blocks for semiconductor nanowire optoelectronic devices on arbitrary substrates.

GaAs nanowires (NWs) are seen as promising building blocks for future optoelectronic devices. To ensure reproducible properties, a high NW uniformity is required. Here, a substantial number of both position-controlled and randomly grown self-catalyzed GaAs/AlGaAs core-shell NWs are compared. Single NWs are characterized by correlated microphotoluminescence (µ-PL) spectroscopy and transmission electron microscopy (TEM). TEM is done in the 110-and 112-projections, and on the 111-cross-section of the NWs. The position-control grown NWs showed a higher degree of uniformity in morphology. All NWs on both samples had a predominantly stacking fault free zinc blende structure, with a main optical response around the GaAs free exciton energy. However, NW-to-NW structural variations in the tip region and radial compositional variations in the shell are present in both samples. These structural features could be the origin of variations in the optical response just below and above the free exciton energy. This correlated study demonstrates that the observed distinct, sharp PL peaks in the 1.6-1.8 eV energy range present in several NWs, are possibly related to radial compositional variations in the AlGaAs shell rather than the structural defects in the tip region.