V. G. Dubrovskii

Semiconductor nanowhiskers: Synthesis, properties, and applications

Recent results of studying the semiconductor’s whisker nanocrystals are reviewed. Physical grounds of growing whisker nanocrystals using the mechanism vapor-liquid-crystal are given and the main epitaxial technologies of synthesis of whisker nanocrystals are described. Thermodynamic and kinetic factors controlling the morphological properties, composition, and crystal structure of whisker nanocrystals are considered in detail. The main theoretical models of the growth and structure of whisker nanocrystals are described. The data on physical properties of whisker nanocrystals and possibilities of their use in nanophotonics, nanoelectronics, and nanobiotechnology are presented.

Au-assisted molecular beam epitaxy of InAs nanowires: Growth and theoretical analysis

The Au-assisted molecular beam epitaxial growth of InAs nanowires is discussed. In situ reflection high-energy electron diffraction observations of phase transitions of the catalyst particles indicate that they can be liquid below the eutectic point of the Au-In alloy. The temperature range where the catalyst can be liquid covers the range where we observed nanowire formation (380–430 °C). The variation of nanowire growth rate with temperature is investigated. Pure axial nanowire growth is observed at high temperature while mixed axial/lateral growth occurs at low temperature. The change of the InAs nanowire shape with growth duration is studied. It is shown that significant lateral growth of the lower part of the nanowire starts when its length exceeds a critical value, so that their shape presents a steplike profile along their axis. A theoretical model is proposed to explain the nanowire morphology as a result of the axial and lateral contributions of the nanowire growth.

New Mode of Vapor−Liquid−Solid Nanowire Growth

We report on the new mode of the vapor-liquid-solid nanowire growth with a droplet wetting the sidewalls and surrounding the nanowire rather than resting on its top. It is shown theoretically that such an unusual configuration happens when the growth is catalyzed by a lower surface energy metal. A model of a nonspherical elongated droplet shape in the wetting case is developed. Theoretical predictions are compared to the experimental data on the Ga-catalyzed growth of GaAs nanowires by molecular beam epitaxy. In particular, it is demonstrated that the experimentally observed droplet shape is indeed nonspherical. The new VLS mode has a major impact on the crystal structure of GaAs nanowires, helping to avoid the uncontrolled zinc blende-wurtzite polytylism under optimized growth conditions. Since the triple phase line nucleation is suppressed on surface energetic grounds, all nanowires acquire pure zinc blende phase along the entire length, as demonstrated by the structural studies of our GaAs nanowires.

Nucleation theory and growth of nanostructures

Foreword by Zh. I. Alferov.- Introduction.- Fundamentals of nucleation theory.- Kinetics of phase transition.- Quantum dots and nanoneedles.- Growth of semiconductor nanowires.- Crystal structure of III-V nanowires.

Growth mechanisms and crystallographic structure of InP nanowires on lattice-mismatched substrates

We present a growth model that predicts the growth phase and mechanism of InP nanowires (NWs) and the experimental verifications of the model. The NWs were grown on lattice-mismatched GaAs substrates using metal-organic chemical vapor deposition via Au nanodrop-assisted vapor-liquid-solid growth. Nanodrops with larger diameters are shown to grow longer NWs because growth is governed mainly by direct precursor impingement on the nanodrop surface. The theoretical and experimental results also show that growth phase is dependent on NW diameter. We show that InP NWs with a diameter less than a certain value exhibit coherent growth of a single crystalline wurtzite (WZ) phase, whereas larger diameter InP NWs often contain sequences of WZ and zincblende phases and stacking faults. These findings allow one to achieve coherent NW growth and WZ phases free from twinning if the NW diameter is below certain material-dependent critical diameters.

Record Pure Zincblende Phase in GaAs Nanowires down to 5 nm in Radius

We report the Au catalyst-assisted synthesis of 20 μm long GaAs nanowires by the vapor-liquid-solid hydride vapor phase epitaxy (HVPE) exhibiting a polytypism-free zincblende phase for record radii lower than 15 nm down to 5 nm. HVPE makes use of GaCl gaseous growth precursors at high mass input of which fast dechlorination at the usual process temperature of 715 °C results in high planar growth rate (standard 30-40 μm/h). When it comes to the vapor-liquid-solid growth of nanowires, fast solidification at a rate higher than 100 μm/h is observed. Nanowire growth by HVPE only proceeds by introduction of precursors in the catalyst droplets from the vapor phase. This promotes almost pure axial growth leading to nanowires with a constant cylinder shape over unusual length. The question of the cubic zincblende structure observed in HVPE-grown GaAs nanowires regardless of their radius is at the heart of the paper. We demonstrate that the vapor-liquid-solid growth in our conditions takes place at high liquid chemical potential that originates from very high influxes of both As and Ga. This yields a Ga concentration systematically higher than 0.62 in the Au-Ga-As droplets. The high Ga concentration decreases the surface energy of the droplets, which disables nucleation at the triple phase line thus preventing the formation of wurtzite structure whatever the nanowire radius is.

Photovoltaic Properties of p-Doped GaAs Nanowire Arrays Grown on n-Type GaAs(111)B Substrate

We report on the molecular beam epitaxy growth of Au-assisted GaAs p-type-doped NW arrays on the n-type GaAs(111)B substrate and their photovoltaic properties. The samples are grown at different substrate temperature within the range from 520 to 580 °C. It is shown that the dependence of conversion efficiency on the substrate temperature has a maximum at the substrate temperature of 550 °C. For the best sample, the conversion efficiency of 1.65% and the fill factor of 25% are obtained.

Scaling growth kinetics of self-induced GaN nanowires

We present a kinetic model showing why self-induced GaN nanowires synthesized by molecular beam epitaxy obey the scaling growth laws. Our model explains the scaling behavior from kinetic considerations of the step flow radial growth and the shadow effect. The nanowire length L and radius R scale with time as [1+C(t-t0)]α/(α+1) and [1+C(t-t0)]1/(α+1), respectively. Consequently, the length scales with the radius as L∝Rα. The power index α equals 2.46 in our conditions. This scaling behavior is paramount for understanding the self-induced growth of nanowires in general as well as for tuning their morphology to the desired properties.

Unconventional growth mechanism for monolithic integration of III-V on silicon.

The heterogeneous integration of III-V optoelectronic devices with Si electronic circuits is highly desirable because it will enable many otherwise unattainable capabilities. However, direct growth of III-V thin film on silicon substrates has been very challenging because of large mismatches in lattice constants and thermal coefficients. Furthermore, the high epitaxial growth temperature is detrimental to transistor performance. Here, we present a detailed studies on a novel growth mode which yields a catalyst-free (Al,In)GaAs nanopillar laser on a silicon substrate by metal-organic chemical vapor deposition at the low temperature of 400 °C. We study the growth and misfit stress relaxation mechanism by cutting through the center of the InGaAs/GaAs nanopillars using focused ion beam and inspecting with high-resolution transmission electron microscopy. The bulk material of the nanopillar is in pure wurtzite crystal phase, despite the 6% lattice mismatch with the substrate, with all stacking disorders well confined in the bottom-most transition region and terminated horizontally. Furthermore, InGaAs was found to be in direct contact with silicon, in agreement with the observed crystal orientation alignment and good electrical conduction across the interface. This is in sharp contrast to many III-V nanowires on silicon which are observed to stem from thin SiN(x), SiO(2), or SiO(2)/Si openings. In addition, GaAs was found to grow perfectly as a shell layer on In(0.2)Ga(0.8)As with an extraordinary thickness, which is 15 times greater than the theoretical thin-film critical thickness for a 1.5% lattice mismatch. This is attributed to the core-shell radial geometry allowing the outer layers to expand and release the strain due to lattice mismatch. The findings in this study redefine the rules for lattice-mismatched growth on heterogeneous substrates and device structure design.

Boron distribution in the core of Si nanowire grown by chemical vapor deposition

The boron dopant distribution in Si nanowires grown by the Au-catalyzed chemical vapor deposition is characterized by laser-assisted atom probe tomography. A convenient and an effective method for performing the atom probe tomography of an individual nanowire is developed. Using this technique, we demonstrate that when Si nanowires are doped with boron at high silane partial pressure, the radial distribution of boron atoms is rather inhomogeneous. Much more boron atoms incorporate at the periphery than in the center, with the concentration increasing by an order of magnitude as the distance from the nanowire axis increases from zero to only 15 nm. A theoretical model is presented that is capable of describing the observed spatial inhomogeneity of boron dopant. We also consider different kinetic pathways of boron incorporation and discuss the values of diffusion length and diffusion coefficients obtained by fitting the experimental data.