Three-dimensional GaN/AlN nanowire heterostructures by separating nucleation and growth processes

Bottom-up nanostructure assembly has been a central theme of materials synthesis over the past few decades. Semiconductor quantum dots and nanowires provide additional degrees of freedom for charge confinement, strain engineering, and surface sensitivity-properties that are useful to a wide range of solid state optical and electronic technologies. A central challenge is to understand and manipulate nanostructure assembly to reproducibly generate emergent structures with the desired properties. However, progress is hampered due to the interdependence of nucleation and growth phenomena. Here we show that by dynamically adjusting the growth kinetics, it is possible to separate the nucleation and growth processes in spontaneously formed GaN nanowires using a two-step molecular beam epitaxy technique. First, a growth phase diagram for these nanowires is systematically developed, which allows for control of nanowire density over three orders of magnitude. Next, we show that by first nucleating nanowires at a low temperature and then growing them at a higher temperature, height and density can be independently selected while maintaining the target density over long growth times. GaN nanowires prepared using this two-step procedure are overgrown with three-dimensionally layered and topologically complex heterostructures of (GaN/AlN). By adjusting the growth temperature in the second growth step either vertical or coaxial nanowire superlattices can be formed. These results indicate that a two-step method allows access to a variety of kinetics at which nanowire nucleation and adatom mobility are adjustable.     

Synergetic nanowire growth

Interest in nanowires continues to grow because they hold the promise of monolithic integration of high-performance semiconductors with new functionality into existing silicon technology. Most nanowires are grown using vapour-liquid-solid growth, and despite many years of study this growth mechanism remains under lively debate. In particular, the role of the metal particle is unclear. For instance, contradictory results have been reported on the effect of particle size on nanowire growth rate. Additionally, nanowire growth from a patterned array of catalysts has shown that small wire-to-wire spacing leads to materials competition and a reduction in growth rates. Here, we report on a counterintuitive synergetic effect resulting in an increase of the growth rate for decreasing wire-to-wire distance. We show that the growth rate is proportional to the catalyst area fraction. The effect has its origin in the catalytic decomposition of precursors and is applicable to a variety of nanowire materials and growth techniques.     

SiGe nanowire growth and characterization

Single-crystal SiGe nanowires were synthesized via the vapour-liquid-solid (VLS) growth mechanism using disilane and germane as precursor gases. We have investigated the effect of temperature, pressure, and the inlet gas ratio on the growth and stoichiometry of Si(x)Ge(1-x) nanowires. The nanowires were characterized using scanning and transmission electron microscopies and energy dispersive x-ray analysis. It was found that nanowires with a Si:Ge ratio of about 1 had smooth surfaces, whereas departure from this ratio led to rough surfaces. Electrical properties were then investigated by fabricating back-gated field effect transistors (using a focused ion beam system) where single SiGe nanowires served as the conduction channels. Gated conduction was observed although resistance in the undoped devices was high.     

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.     

Modeling GaN nanowire growth on silicon

We have developed a kinetic theory of the growth of self-induced GaN nanowires (NWs) in the vertical and lateral directions on substrates with amorphous sublayers. A model is constructed that can describe temporal evolution of the NW length and radius. The results of model calculations are compared to experimental data on temporal dependences of the length and radius of GaN nanowires grown on amorphous Si _x N _y sublayers on Si substrates. The comparison shows good agreement between the proposed theory and experiment. Conditions, for which the NW length and radius are described by power functions of the time and the NW length exhibits scaling superlinear dependence on the radius, are determined.     

ZnO纳米线阵列的图形化生长

采用光刻和射频磁控溅射技术在Si衬底上制备了图形化的ZnO种子层薄膜。分别采用气相榆运和水热合成法，制备了最小单元为30μm的图形化的ZnO纳米线阵列。X射线衍射（XRD）分析显示单晶纳米线阵列具有高度的c轴[001]择优取向生长性质，从扫描电子显微镜（SEM）照片看出，阵列图形完整清晰，边缘整齐，纳米线阵列在室温下光致发光（PL）谱线中在380hm左右具有强烈的紫外发射峰，可见光区域发射峰得到了抑制，证明ZnO纳米线阵列氧空位缺陷少，晶体质量高。     

Elementary processes in prebreakdown phenomena in the atmosphere

The effect of negative oxygen ion destruction upon breakdown conditions in atmospheric air is analyzed. It is shown that ozone accumulation due to plasmochemical reactions occurring in ionized air produces a reduction in the breakdown voltage, related to negative O^– ion destruction upon collision with ozone molecules under realistic conditions. A relationship is derived for electric field breakdown intensity and ozone molecule lifetime for the real atmosphere.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 62, No. 5 pp. 661–664, May, 1992.     

Temperature-dependent nonradiative recombination processes in GaN-based nanowire white-light-emitting diodes on silicon

In this paper, we have performed a detailed investigation of the temperature- and current-dependent emission characteristics of nanowire light-emitting diodes, wherein InGaN/GaN dot-in-a-wire nanoscale heterostructures and a p-doped AlGaN electron blocking layer are incorporated in the device's active region to achieve white-light emission and to prevent electron overflow, respectively. Through these studies, the Auger coefficient is estimated to be in the range of ～10(-34) cm(6) s(-1) or less, which is nearly four orders of magnitude smaller than the commonly reported values of planar InGaN/GaN heterostructures, suggesting Auger recombination plays an essentially negligible role in the performance of GaN-based nanowire light-emitting diodes. It is observed, however, that the performance of such nanowire LEDs suffers severely from Shockley-Read-Hall recombination, which can account for nearly 40% of the total carrier recombination under moderate injection conditions (～100 A cm(-2)) at room temperature. The Shockley-Read-Hall nonradiative lifetime is estimated to be in the range of a few nanoseconds at room temperature, which correlates well with the surface recombination velocity of GaN and the wire diameters used in this experiment.     

Shape-controlled Au particles for InAs nanowire growth

We present a study of InAs nanowire (NW) growth with shape-controlled Au seed particles. In comparison to more conventional spherical particles, the highly faceted, shaped Au particles are found to enhance the initial growth kinetics of InAs NWs at identical growth conditions. Analysis of the NWs after growth by transmission electron microscopy and energy-dispersive spectroscopy suggests that while In diffuses into the bulk of the shaped Au particles, in accordance with the vapor-liquid-solid (VLS) growth mechanism, the surface faceting is preserved. A key difference is that the shaped Au particles are characterized by a thicker In shell on their surfaces than the spherical Au particles, indicating that increased adsorption of In leads to the observed growth rate enhancement. On the basis of these results, we propose that our picture of VLS growth in regards to liquefaction and droplet formation is incomplete and that the initial particle morphology can be used to tailor NW growth.     

Multiplicity of steady modes of nanowire growth

For nanowire growth by the vapor-liquid-solid process, we examine whether there is a unique steady-state growth morphology. Applying a continuum model for faceted nanowire evolution to a model crystal structure, we enumerate the possible growth morphologies and calculate their dynamical stability. We find that even for a single set of experimental conditions there can be multiple distinct modes of steady-state growth. The actual growth mode occurring in experiment thus depends on the initial conditions and growth history. Relevant experiments are discussed.     

Catalyst incorporation at defects during nanowire growth

Scanning and transmission electron microscopy was used to correlate the structure of planar defects with the prevalence of Au catalyst atom incorporation in Si nanowires. Site-specific high-resolution imaging along orthogonal zone axes, enabled by advances in focused ion beam cross sectioning, reveals substantial incorporation of catalyst atoms at grain boundaries in <110> oriented nanowires. In contrast, (111) stacking faults that generate new polytypes in <112> oriented nanowires do not show preferential catalyst incorporation. Tomographic reconstruction of the catalyst-nanowire interface is used to suggest criteria for the stability of planar defects that trap impurity atoms in catalyst-mediated nanowires.     

Vertical ZnO nanowire growth on metal substrates

Vertical growth of ZnO nanowires is usually achieved on lattice-matched substrates such as ZnO or sapphire using various vapor transport techniques. Accomplishing this on silicon substrates requires thick ZnO buffer layers. Here we demonstrate growth of vertical ZnO nanowires on FeCrAl substrates. The pre-annealing prior to growth appears to preferentially segregate Al and O to the surface, thus leading to a self-forming, thin pseudo-buffer layer, which then results in vertical nanowire growth as on sapphire substrates. Metal substrates are more suitable and cheaper than others for applications in piezoelectric devices, and thin self-forming layers can also reduce interfacial resistance to electrical and thermal conduction.     

Control of Si nanowire growth by oxygen

Semiconductor nanowires formed using the vapor-liquid-solid mechanism are routinely grown in many laboratories, but a comprehensive understanding of the key factors affecting wire growth is still lacking. In this paper we show that, under conditions of low disilane pressure and higher temperature, long, untapered Si wires cannot be grown, using Au catalyst, without the presence of oxygen. Exposure to oxygen, even at low levels, reduces the diffusion of Au away from the catalyst droplets. This allows the droplet volumes to remain constant for longer times and therefore permits the growth of untapered wires. This effect is observed for both gas-phase and surface-bound oxygen, so the source of oxygen is unimportant. The control of oxygen exposure during growth provides a new tool for the fabrication of long, uniform-diameter structures, as required for many applications of nanowires.     

Solid-phase diffusion mechanism for GaAs nanowire growth

Controllable production of nanometre-sized structures is an important field of research, and synthesis of one-dimensional objects, such as nanowires, is a rapidly expanding area with numerous applications, for example, in electronics, photonics, biology and medicine. Nanoscale electronic devices created inside nanowires, such as p-n junctions, were reported ten years ago. More recently, hetero-structure devices with clear quantum-mechanical behaviour have been reported, for example the double-barrier resonant tunnelling diode and the single-electron transistor. The generally accepted theory of semiconductor nanowire growth is the vapour-liquid-solid (VLS) growth mechanism, based on growth from a liquid metal seed particle. In this letter we suggest the existence of a growth regime quite different from VLS. We show that this new growth regime is based on a solid-phase diffusion mechanism of a single component through a gold seed particle, as shown by in situ heating experiments of GaAs nanowires in a transmission electron microscope, and supported by highly resolved chemical analysis and finite element calculations of the mass transport and composition profiles.     

单晶铋纳米线阵列的可控生长

采用脉冲电化学沉积技术,利用同一直径的氧化铝模板,通过调节脉冲参数制备出了不同直径的单晶铋纳米线阵列,同时实现了纳米线取向的可控生长.保持脉冲弛豫时间不变,纳米线的直径随着脉冲沉积时间的增加而变大,纳米线的取向随着脉冲占空比的变化发生移动.     

Large-scale solution-phase growth of Cu-doped ZnO nanowire networks

Film-like networks of Cu-doped (0.8-2.5 at.%) ZnO nanowires were successfully synthesized through a facile solution process at a low temperature (<100 degrees C). The pH value of solution plays a key role in controlling the density and quality of the Cu-doped ZnO nanowires and the dopant concentration of ZnO nanowires was controlled by adjusting the Cu2+/Zn2+ concentration ratio during the synthesis. The structural study showed that the as-prepared Cu-doped ZnO nanowires with a narrow diameter range of 20-30 nm were single crystal and grew along [0001] direction. Photoluminescence and electrical conductivity measurements showed that Cu doping can lead to a redshift in bandgap energy and an increase in the resistivity of ZnO. The thermal annealing of the as-grown nanowires at a low temperature (300 degrees C) decreased the defect-related emission within the visible range and increased the electrical conductivity. The high-quality ZnO nanowire network with controlled doping will enable further application to flexible and transparent electronics.     

Ledge-flow-controlled catalyst interface dynamics during Si nanowire growth

Self-assembled nanowires offer the prospect of accurate and scalable device engineering at an atomistic scale for applications in electronics, photonics and biology. However, deterministic nanowire growth and the control of dopant profiles and heterostructures are limited by an incomplete understanding of the role of commonly used catalysts and specifically of their interface dynamics. Although catalytic chemical vapour deposition of nanowires below the eutectic temperature has been demonstrated in many semiconductor-catalyst systems, growth from solid catalysts is still disputed and the overall mechanism is largely unresolved. Here, we present a video-rate environmental transmission electron microscopy study of Si nanowire formation from Pd silicide crystals under disilane exposure. A Si crystal nucleus forms by phase separation, as observed for the liquid Au-Si system, which we use as a comparative benchmark. The dominant coherent Pd silicide/Si growth interface subsequently advances by lateral propagation of ledges, driven by catalytic dissociation of disilane and coupled Pd and Si diffusion. Our results establish an atomistic framework for nanowire assembly from solid catalysts, relevant also to their contact formation.     

Controlling silicon nanowire growth direction via surface chemistry

We report on the first in situ chemical investigation of vapor-liquid-solid semiconductor nanowire growth and reveal the important, and previously unrecognized, role of transient surface chemistry near the triple-phase line. Real-time infrared spectroscopy measurements coupled with postgrowth electron microscopy demonstrate that covalently bonded hydrogen atoms are responsible for the (left angle bracket 111 right angle bracket) to (left angle bracket 112 right angle bracket) growth orientation transition commonly observed during Si nanowire growth. Our findings provide insight into the root cause of this well-known nanowire growth phenomenon and open a new route to rationally engineer the crystal structure of these nanoscale semi-conductors.