Focused ion beam lithography for position-controlled nanowire growth.

To exploit the promising properties of semiconductor nanowires and ensure the uniformity required to achieve device integration, their position on the growth substrate must be controlled. This work demonstrates the direct patterning of a SiO2/Si substrate using focused ion beam (FIB) patterning to control self-catalyzed GaAsSb nanowire growth in molecular beam epitaxy (MBE). Besides position control, FIB patterning parameters influence nanowire yield, composition and structure. Total ion dose per hole is found to be the most important parameter. Yield of single nanowires ranges from ≈34% to ≈83%, with larger holes dominated by multiple nanowires per hole. Areas exposed to low ion beam doses are selectively etched by routine pre-MBE HF cleaning, enabling patterning and nanowire nucleation with minimal damage to the Si substrate. The optical and electronic properties of nanowires are found to depend on the ion dose used during patterning, indicating the potential for FIB patterning to tune nanowire properties. These findings demonstrate the possibility for a FIB lithography protocol which could provide a rapid and direct patterning process for flexible controlled nanowire growth.

The influence of AlN buffer layer on the growth of self-assembled GaN nanocolumns on graphene.

GaN nanocolumns were synthesized on single-layer graphene via radio-frequency plasma-assisted molecular beam epitaxy, using a thin migration-enhanced epitaxy (MEE) AlN buffer layer as nucleation sites. Due to the weak nucleation on graphene, instead of an AlN thin-film we observe two distinguished AlN formations which affect the subsequent GaN nanocolumn growth: (i) AlN islands and (ii) AlN nanostructures grown along line defects (grain boundaries or wrinkles) of graphene. Structure (i) leads to the formation of vertical GaN nanocolumns regardless of the number of AlN MEE cycles, whereas (ii) can result in random orientation of the nanocolumns depending on the AlN morphology. Additionally, there is a limited amount of direct GaN nucleation on graphene, which induces non-vertical GaN nanocolumn growth. The GaN nanocolumn samples were characterized by means of scanning electron microscopy, transmission electron microscopy, high-resolution X-ray diffraction, room temperature micro-photoluminescence, and micro-Raman measurements. Surprisingly, the graphene with AlN buffer layer formed using less MEE cycles, thus resulting in lower AlN coverage, has a lower level of nitrogen plasma damage. The AlN buffer layer with lowest AlN coverage also provides the best result with respect to high-quality and vertically-aligned GaN nanocolumns.

Single GaAs Nanowire/Graphene Hybrid Devices Fabricated by a Position-Controlled Microtransfer and an Imprinting Technique for an Embedded Structure.

We developed a new technique to fabricate single nanowire devices with reliable graphene/nanowire contacts using a position-controlled microtransfer and an embedded nanowire structure in a planar junction configuration. A thorough study of electrical properties and fabrication challenges of single p-GaAs nanowire/graphene devices was carried out in two different device configurations: (1) a graphene bottom-contact device where the nanowire-graphene contact junction is formed by transferring a nanowire on top of graphene and (2) a graphene top-contact device where the nanowire-graphene contact junction is formed by transferring graphene on top of an embedded nanowire. For the graphene top-contact devices, graphene-nanowire-metal devices, where graphene is used as one electrode and metal is the other electrode to a nanowire, and graphene-nanowire-graphene devices, where both electrodes to a nanowire are graphene, were investigated and compared with conventional metal/p-GaAs nanowire devices. Conventional metal/p-GaAs nanowire contact devices were further investigated in embedded and nonembedded nanowire device configurations. A significantly improved current in the embedded device configuration is explained with a "parallel resistors model" where the high-resistance parts with the metal-semiconductor Schottky contact and the low-resistance parts with noncontacted facets of the hexagonal nanowires are taken into consideration. Consistently, the nonembedded nanowire structure is found to be depleted much easier than the embedded nanowires from which an estimation for a fully depleted condition has also been established.

Epitaxially grown III-arsenide-antimonide nanowires for optoelectronic applications.

Epitaxially grown ternary III-arsenide-antimonide (III-As-Sb) nanowires (NWs) are increasingly attracting attention due to their feasibility as a platform for the integration of largely lattice-mismatched antimonide-based heterostructures while preserving the high crystal quality. This and the inherent bandgap tuning flexibility of III-As-Sb in the near- and mid-infrared wavelength regions are important and auspicious premises for a variety of optoelectronic applications. In this review, we summarize the current understanding of the nucleation, morphology-change and crystal phase evolution of GaAsSb and InAsSb NWs and their characterization, especially in relation to Sb incorporation during growth. By linking these findings to the optical properties in such ternary NWs and their heterostructures, a brief account of the ongoing development of III-As-Sb NW-based photodetectors and light emitters is also given.

GaN/AlGaN Nanocolumn Ultraviolet Light-Emitting Diode Using Double-Layer Graphene as Substrate and Transparent Electrode.

The many outstanding properties of graphene have impressed and intrigued scientists for the last few decades. Its transparency to light of all wavelengths combined with a low sheet resistance makes it a promising electrode material for novel optoelectronics. So far, no one has utilized graphene as both the substrate and transparent electrode of a functional optoelectronic device. Here, we demonstrate the use of double-layer graphene as a growth substrate and transparent conductive electrode for an ultraviolet light-emitting diode in a flip-chip configuration, where GaN/AlGaN nanocolumns are grown as the light-emitting structure using plasma-assisted molecular beam epitaxy. Although the sheet resistance is increased after nanocolumn growth compared with pristine double-layer graphene, our experiments show that the double-layer graphene functions adequately as an electrode. The GaN/AlGaN nanocolumns are found to exhibit a high crystal quality with no observable defects or stacking faults. Room-temperature electroluminescence measurements show a GaN related near bandgap emission peak at 365 nm and no defect-related yellow emission.

Vertical GaN nanocolumns grown on graphene intermediated with a thin AlN buffer layer.

We report on the self-assembled growth of high-density and vertically-oriented n-doped GaN nanocolumns on graphene by radio-frequency plasma-assisted molecular beam epitaxy. Graphene was transferred to silica glass, which was used as the substrate carrier. Using a migration enhanced epitaxy grown AlN buffer layer for the nucleation is found to enable a high density of vertical GaN nanocolumns with c-axis growth orientation on graphene. Furthermore, micro-Raman spectroscopy indicates that the AlN buffer reduces damage on the graphene caused by impinging active N species generated by the radio-frequency plasma source during the initial growth stage and nucleation of GaN. In addition, the grown GaN nanocolumns on graphene are found to be virtually stress-free. Micro-photoluminescence measurements show near band-edge emission from wurtzite GaN, exhibiting higher GaN bandgap related photoluminescence intensity relative to a reference GaN bulk substrate and the absence of both yellow luminescence and excitonic defect emission. Transmission electron microscopy reveals the interface of GaN nanocolumns on graphene via a thin AlN buffer layer. Even though the first few monolayers of AlN on top of graphene are strained due to in-plane lattice mismatch between AlN and graphene, the grown GaN nanocolumns have a wurtzite crystal structure without observable defects. The results of this initial work pave the way towards realizing low-cost and high-performance electronic and optoelectronic devices based on III-N semiconductors grown on graphene.

Single-Mode Near-Infrared Lasing in a GaAsSb-Based Nanowire Superlattice at Room Temperature.

Semiconductor nanowire lasers can produce guided coherent light emission with miniaturized geometry, bringing about new possibilities for a variety of applications including nanophotonic circuits, optical sensing, and on-chip and chip-to-chip optical communications. Here, we report on the realization of single-mode and room-temperature lasing from 890 to 990 nm, utilizing a novel design of single nanowires with GaAsSb-based multiple axial superlattices as a gain medium under optical pumping. The control of lasing wavelength via compositional tuning with excellent room-temperature lasing performance is shown to result from the unique nanowire structure with efficient gain material, which delivers a low lasing threshold of ∼6 kW/cm2 (75 µJ/cm2 per pulse), a lasing quality factor as high as 1250, and a high characteristic temperature of ∼129 K. These results present a major advancement for the design and synthesis of nanowire laser structures, which can pave the way toward future nanoscale integrated optoelectronic systems with superior performance.

Low frequency noise in single GaAsSb nanowires with self-induced compositional gradients.

Due to bandgap tunability, GaAsSb nanowires (NWs) have received a great deal of attention for a variety of optoelectronic device applications. However, electrical and optical properties of GaAsSb are strongly affected by Sb-related defects and scattering from surface states and/or defects, which can limit the performance of GaAsSb NW devices. Thus, in order to utilize the GaAsSb NWs for high performance electronic and optoelectronic devices, it is required to study the material and interface properties (e.g. the interface trap density) in the GaAsSb NW devices. Here, we investigate the low frequency noise in single GaAsSb NWs with self-induced compositional gradients. The current noise spectral density of the GaAsSb NW device showed a typical 1/f noise behavior. The Hooge's noise parameter and the interface trap density of the GaAsSb NW device were found to be ∼2.2 × 10(-2) and ∼2 × 10(12) eV(-1) cm(-2), respectively. By applying low frequency noise measurements, the noise equivalent power, a key figure of merit of photodetectors, was calculated. The observed low frequency noise properties can be useful as guidance for quality and reliability of GaAsSb NW based electronic devices, especially for photodetectors.

In Situ Heat-Induced Replacement of GaAs Nanowires by Au.

Here we report on the heat-induced solid-state replacement of GaAs by Au in nanowires. Such replacement of semiconductor nanowires by metals is envisioned as a method to achieve well-defined junctions within nanowires. To better understand the mechanisms and dynamics that govern the replacement reaction, we performed in situ heating studies using high-resolution scanning transmission electron microscopy. The dynamic evolution of the phase boundary was investigated, as well as the crystal structure and orientation of the different phases at reaction temperatures. In general, the replacement proceeds one GaAs(111) bilayer at a time, and no fixed epitaxial relation could be found between the two phases. The relative orientation of the phases affects the replacement dynamics and can induce growth twins in the Au nanowire phase. In the case of a limited Au supply, the metal phase can also become liquid.

Vertically Oriented Growth of GaN Nanorods on Si Using Graphene as an Atomically Thin Buffer Layer.

The monolithic integration of wurtzite GaN on Si via metal-organic vapor phase epitaxy is strongly hampered by lattice and thermal mismatch as well as meltback etching. This study presents single-layer graphene as an atomically thin buffer layer for c-axis-oriented growth of vertically aligned GaN nanorods mediated by nanometer-sized AlGaN nucleation islands. Nanostructures of similar morphology are demonstrated on graphene-covered Si(111) as well as Si(100). High crystal and optical quality of the nanorods are evidenced through scanning transmission electron microscopy, micro-Raman, and cathodoluminescence measurements supported by finite-difference time-domain simulations. Current-voltage characteristics revealed high vertical conduction of the as-grown GaN nanorods through the Si substrates. These findings are substantial to advance the integration of GaN-based devices on any substrates of choice that sustains the GaN growth temperatures, thereby permitting novel designs of GaN-based heterojunction device concepts.

New Insights into the Origins of Sb-Induced Effects on Self-Catalyzed GaAsSb Nanowire Arrays.

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.

Rectifying Single GaAsSb Nanowire Devices Based on Self-Induced Compositional Gradients.

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.

Self-catalyzed MBE grown GaAs/GaAs(x)Sb(1-x) core-shell nanowires in ZB and WZ crystal structures.

We have investigated the growth of self-catalyzed GaAs/GaAs(x)Sb(1-x) core-shell nanowires directly on Si(111) substrates by molecular beam epitaxy. The compositions of the GaAs(x)Sb(1-x) shells are tuned in a wide range where the Sb-content is varied from 10 to ~70%, covering the miscibility gap. In addition, the GaAs(x)Sb(1-x) shells are grown on both zinc blende (ZB) and wurtzite (WZ) crystal structures. Morphological and structural characterizations of the grown nanowires indicate successful transfer of the GaAs core crystal structure to the GaAs(x)Sb(1-x) shells for both ZB and WZ nanowires, with slower shell growth rate on the WZ segments.

A story told by a single nanowire: optical properties of wurtzite GaAs.

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.

Vertically aligned GaAs nanowires on graphite and few-layer graphene: generic model and epitaxial growth.

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.

Effects of substrate annealing on the gold-catalyzed growth of ZnO nanostructures.

The effects of thermal substrate pretreatment on the growth of Au-catalyzed ZnO nanostructures by pulsed laser deposition are investigated. C-plane sapphire substrates are annealed prior to deposition of a thin Au layer. Subsequent ZnO growths on substrates annealed above 1,200°C resulted in a high density of nanosheets and nanowires, whereas lower temperatures led to low nanostructure densities. Separate Au film annealing experiments at 700°C showed little variation in the size and density of the Au catalyst droplets with substrate annealing temperature. The observed variation in the density of nanostructures is attributed to the number of surface nucleation sites on the substrate, leading to a competition between nucleation promoted by the Au catalyst and surface nucleation sites on the rougher surfaces annealed below 1,200°C.

Engineering parallel and perpendicular polarized photoluminescence from a single semiconductor nanowire by crystal phase control.

We report on a crystal phase-dependent photoluminescence (PL) polarization effect in individual wurtzite GaAs nanowires with a zinc blende GaAsSb insert grown by Au-assisted molecular beam epitaxy. The PL emission from the zinc blende GaAsSb insert is strongly polarized along the nanowire axis while the emission from the wurtzite GaAs nanowire is perpendicularly polarized. The results indicate that the crystal phases, through optical selection rules, are playing an important role in the alignment of the PL polarization in nanowires besides the linear polarization induced by the dielectric mismatch. The strong excitation power dependence and long recombination lifetimes ( approximately 4 ns) from the wurtzite GaAs and zinc blende GaAsSb-related PL emission strongly indicate the existence of type II band alignments in the nanowire due to the presence of nanometer thin zinc blende segments and stacking faults in the wurtzite GaAs barrier.

Growth and characterization of wurtzite GaAs nanowires with defect-free zinc blende GaAsSb inserts.

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.