Taper-free and vertically oriented Ge nanowires on Ge/Si substrates grown by a two-temperature process

Taper-free and vertically oriented Ge nanowires were grown on Si (111) substrates by chemical vapor deposition with Au nanoparticle catalysts. To achieve vertical nanowire growth on the highly lattice mismatched Si substrate, a thin Ge buffer layer was first deposited, and to achieve taper-free nanowire growth, a two-temperature process was employed. The two-temperature process consisted of a brief initial base growth step at high temperature followed by prolonged growth at lower temperature. Taper-free and defect-free Ge nanowires grew successfully even at 270 °C, which is 90 °C lower than the bulk eutectic temperature. The yield of vertical and taper-free nanowires is over 90%, comparable to that of vertical but tapered nanowires grown by the conventional one-temperature process. This method is of practical importance and can be reliably used to develop novel nanowire-based devices on relatively cheap Si substrates. Additionally, we observed that the activation energy of Ge nanowire growth by the two-temperature process is dependent on Au nanoparticle size. The low activation energy (∼5 kcal/mol) for 30 and 50 nm diameter Au nanoparticles suggests that the decomposition of gaseous species on the catalytic Au surface is a rate-limiting step. A higher activation energy (∼14 kcal/mol) was determined for 100 nm diameter Au nanoparticles which suggests that larger Au nanoparticles are partially solidified and that growth kinetics become the rate-limiting step. © 2011 American Chemical Society.

Defect-free GaAs/AlGaAs Core-shell nanowires on Si substrates

We report straight and vertically aligned defect-free GaAs nanowires grown on Si(111) substrates by metal-organic chemical vapor deposition. By deposition of thin GaAs buffer layers on Si substrates, these nanowires could be grown on the buffer layers with much less stringent conditions as otherwise imposed by epitaxy of III-V compounds on Si. Also, crystal-defect-free GaAs nanowires were grown by using either a two-temperature growth mode consisting of a short initial nucleation step under higher temperature followed by subsequent growth under lower temperature or a rapid growth rate mode with high source flow rate. These two growth modes not only eliminated planar crystallographic defects but also significantly reduced tapering. Core-shell GaAs-AlGaAs nanowires grown by the two-temperature growth mode showed improved optical properties with strong photoluminescence and long carrier life times. © 2011 American Chemical Society.

Tailoring GaAs, InAs, and InGaAs nanowires for optoelectronic device applications

GaAs, InAs, and InGaAs nanowires each exhibit significant potential to drive new applications in electronic and optoelectronic devices. Nevertheless, the development of these devices depends on our ability to fabricate these nanowires with tight control over critical properties, such as nanowire morphology, orientation, crystal structure, and chemical composition. Although GaAs and InAs are related material systems, GaAs and InAs nanowires exhibit very different growth behaviors. An understanding of these growth behaviors is imperative if high-quality ternary InGaAs nanowires are to be realized. This report examines GaAs, InAs, and InGaAs nanowires, and how their growth may be tailored to achieve desirable material properties. GaAs and InAs nanowire growth are compared, with a view toward the growth of high-quality InGaAs nanowires with device-accessible properties. © 2011 IEEE.

III-V semiconductor nanowires for optoelectronic device applications

Semiconductor nanowires have recently emerged as a new class of materials with significant potential to reveal new fundamental physics and to propel new applications in quantum electronic and optoelectronic devices. Semiconductor nanowires show exceptional promise as nanostructured materials for exploring physics in reduced dimensions and in complex geometries, as well as in one-dimensional nanowire devices. They are compatible with existing semiconductor technologies and can be tailored into unique axial and radial heterostructures. In this contribution we review the recent efforts of our international collaboration which have resulted in significant advances in the growth of exceptionally high quality IIIV nanowires and nanowire heterostructures, and major developments in understanding the electronic energy landscapes of these nanowires and the dynamics of carriers in these nanowires using photoluminescence, time-resolved photoluminescence and terahertz conductivity spectroscopy. © 2011 Elsevier Ltd. All rights reserved.

Structural and optical characterization of vertical GaAs/GaP core-shell nanowires grown on Si substrates

GaAs nanowires were grown on Si (111) substrates. By coating a thin GaAs buffer layer on Si surface and using a two-temperature growth, the morphology and crystal structure of GaAs nanowires were dramatically improved. The strained GaAs/GaP core-shell nanowires, based on the improved GaAs nanowires with a shell thickness of 25 nm, showed a significant shift in emission energy of 260 meV from the unstrained GaAs nanowires. © 2010 IEEE.

Chemical nano-gardens: growth of salt nanowires from supramolecular self-assembly gels.

In this article, we examine the phenomenon of single-crystal halide salt wire growth at the surface of porous materials. We report the use of a single-step casting technique with a supramolecular self-assembly gel matrix that upon drying leads to the growth of single-crystal halide (e.g., NaCl, KCl, and KI) nanowires with diameters ~130-200 nm. We demonstrate their formation using electron microscopy and electron-dispersive X-ray spectroscopy, showing that the supramolecular gel stabilizes the growth of these wires by facilitating a diffusion-driven base growth mechanism. Critically, we show that standard non-supramolecular gels are unable to facilitate nanowire growth. We further show that these nanowires can be grown by seeding, forming nanocrystal gardens. This study helps understand the possible prefunctionalization of membranes to stimulate ion-specific filters or salt efflorescence suppressors, while also providing a novel route to nanomaterial growth.

Imaging and optical properties of single core-shell GaAs-AlGaAs nanowires

We study the optical properties of a single core-shell GaAs-AlGaAs nanowire (grown by VLS method) using the technique of micro-photoluminescence and spatially-resolved photoluminescence imaging. We observe large linear polarization anisotropy in emission and excitation of nanowires.

Phase separation induced by Au catalysts in ternary InGaAs nanowires.

We report a novel phase separation phenomenon observed in the growth of ternary In(x)Ga(1-x)As nanowires by metalorganic chemical vapor deposition. A spontaneous formation of core-shell nanowires is investigated by cross-sectional transmission electron microscopy, revealing the compositional complexity within the ternary nanowires. It has been found that for In(x)Ga(1-x)As nanowires high precursor flow rates generate ternary In(x)Ga(1-x)As cores with In-rich shells, while low precursor flow rates produce binary GaAs cores with ternary In(x)Ga(1-x)As shells. First-principle calculations combined with thermodynamic considerations suggest that this phenomenon is due to competitive alloying of different group-III elements with Au catalysts, and variations in elemental concentrations of group-III materials in the catalyst under different precursor flow rates. This study shows that precursor flow rates are critical factors for manipulating Au catalysts to produce nanowires of desired composition.

Removal of surface states and recovery of band-edge emission in InAs nanowires through surface passivation.

Surface states in semiconductor nanowires (NWs) are detrimental to the NW optical and electronic properties and to their light emission-based applications, due to the large surface-to-volume ratio of NWs and the congregation of defects states near surfaces. In this paper, we demonstrated an effective approach to eliminate surface states in InAs NWs of zinc-blende (ZB) and wurtzite (WZ) structures and a dramatic recovery of band edge emission through surface passivation with organic sulfide octadecylthiol (ODT). Microphotoluminescence (PL) measurements were carried out before and after passivation to study the dominant recombination mechanisms and surface state densities of the NWs. For WZ-NWs, we show that the passivation removed the surface states and recovered the band-edge emission, leading to a factor of ∼19 reduction of PL linewidth. For ZB-NWs, the deep surface states were removed and the PL peaks width became as narrow as ∼250 nm with some remaining emission of near band-edge surface states. The passivated NWs showed excellent stability in atmosphere, water, and heat environments. In particular, no observable changes occurred in the PL features from the passivated NWs exposed in air for more than five months.

Self-healing of fractured GaAs nanowires.

In-situ deformation experiments were carried out in a transmission electron microscope to investigate the structural response of single crystal GaAs nanowires (NWs) under compression. A repeatable self-healing process was discovered in which a partially fractured GaAs NW restored its original single crystal structure immediately after an external compressive force was removed. Possible mechanisms of the self-healing process are discussed.

Vertically oriented epitaxial germanium nanowires on silicon substrates using thin germanium buffer layers.

We demonstrate a method to realize vertically oriented Ge nanowires on Si(111) substrates. Ge nanowires were grown by chemical vapor deposition using Au nanoparticles to seed nanowire growth via a vapor-liquid-solid growth mechanism. Rapid oxidation of Si during Au nanoparticle application inhibits the growth of vertically oriented Ge nanowires directly on Si. The present method employs thin Ge buffer layers grown at low temperature less than 600 degrees C to circumvent the oxidation problem. By using a thin Ge buffer layer with root-mean-square roughness of approximately 2 nm, the yield of vertically oriented Ge nanowires is as high as 96.3%. This yield is comparable to that of homoepitaxial Ge nanowires. Furthermore, branched Ge nanowires could be successfully grown on these vertically oriented Ge nanowires by a secondary seeding technique. Since the buffer layers are grown under moderate conditions without any high temperature processing steps, this method has a wide process window highly suitable for Si-based microelectronics.

Phase perfection in zinc Blende and Wurtzite III-V nanowires using basic growth parameters.

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.

Novel growth and properties of GaAs nanowires on Si substrates.

Straight, vertically aligned GaAs nanowires were grown on Si(111) substrates coated with thin GaAs buffer layers. We find that the V/III precursor ratio and growth temperature are crucial factors influencing the morphology and quality of buffer layers. A double layer structure, consisting of a thin initial layer grown at low V/III ratio and low temperature followed by a layer grown at high V/III ratio and high temperature, is crucial for achieving straight, vertically aligned GaAs nanowires on Si(111) substrates. An in situ annealing step at high temperature after buffer layer growth improves the surface and structural properties of the buffer layer, which further improves the morphology of the GaAs nanowire growth. Through such optimizations we show that vertically aligned GaAs nanowires can be fabricated on Si(111) substrates and achieve the same structural and optical properties as GaAs nanowires grown directly on GaAs(111)B substrates.