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Particle-assisted III-V semiconductor nanowire growth and applications thereof have been studied extensively. However, the stability of nanowires in contact with the particle and the particle chemical composition as a function of temperature remain largely unknown. In this work, we use in situ transmission electron microscopy to investigate the interface between a Au-Ga particle and the top facet of an ?1 1 1 ?-oriented GaAs nanowire grown via the vapor-liquid-solid process. We observed a thermally activated bilayer-by-bilayer removal of the GaAs facet in contact with the liquid particle during annealing between 300 and 420 °C in vacuum. Interestingly, the GaAs-removal rates initially depend on the thermal history of the sample and are time-invariant at later times. In situ X-ray energy dispersive spectroscopy was also used to determine that the Ga content in the particle at any given temperature remains constant over extended periods of time and increases with increasing temperature from 300 to 400 °C. We attribute the observed phenomena to droplet-assisted decomposition of GaAs at a rate that is controlled by the amount of Ga in the droplet. We suggest that the observed transients in removal rates are a direct consequence of time-dependent changes in the Ga content. Our results provide new insights into the role of droplet composition on the thermal stability of GaAs nanowires and complement the existing knowledge on the factors influencing nanowire growth. Moreover, understanding the nanowire stability and decomposition is important for improving processing protocols for the successful fabrication and sustained operation of nanowire-based devices. (Less)

Growing GaAs nanowires with well-defined crystal structures is a challenging task, but may be required for the fabrication of future devices. In terms of crystal phase selection, the connection between theory and experiment is limited, leaving experimentalists with a trial and error approach to achieve the desired crystal structures. In this work, we present a modeling approach designed to provide the missing connection, combining classical nucleation theory, stochastic simulation, and mass transport through the seed particle. The main input parameters for the model are the flows of the growth species and the temperature of the process, giving the simulations the same flexibility as experimental growth. The output of the model can also be directly compared to experimental observables, such as crystal structure of each bilayer throughout the length of the nanowire and the composition of the seed particle. The model thus enables for observed experimental trends to be directly explored theoretically. Here, we use the model to simulate nanowire growth with varying As flows, and our results match experimental trends with a good agreement. By analyzing the data from our simulation, we find theoretical explanations for these experimental results, providing new insights into how the crystal structure is affected by the experimental parameters available for growth.

We use crystal-phase tuning during epitaxial growth of InAs nanowires to create quantum dots with very strong confinement. A set of gate electrodes are used to reproducibly split the quantum dots into even smaller pairs for which we can control the populations down to the last electron. The double quantum dots, which are parallel-coupled to source and drain, show clear and stable odd-even level pairing due to spin degeneracy and the strong confinement. The combination of hard-wall barriers to source and drain, shallow interdot tunnel barriers, and very high single-particle excitation energies allow an order of magnitude tuning of the strength for the first intramolecular bond. We show examples for nanowires with different facet orientations, and suggest possible mechanisms behind the reproducible double-dot formation.

Over the past decade, III-V heterostructure nanowires have attracted a surge of attention for their application in novel semiconductor devices such as tunneling field-effect transistors (TFETs). The functionality of such devices critically depends on the specific atomic arrangement at the semiconductor heterointerfaces. However, most of the currently available characterization techniques lack sufficient spatial resolution to provide local information on the atomic structure and composition of these interfaces. Atomic-resolution spectrum imaging by means of electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM) is a powerful technique with the potential to resolve structure and chemical composition with sub-angstrom spatial resolution and to provide localized information about the physical properties of the material at the atomic scale. Here, we demonstrate the use of atomic-resolution EELS to understand the interface atomic arrangement in three-dimensional heterostructures in semiconductor nanowires. We observed that the radial interfaces of GaSb-InAs heterostructure nanowires are atomically abrupt, while the axial interface in contrast consists of an interfacial region where intermixing of the two compounds occurs over an extended spatial region. The local atomic configuration affects the band alignment at the interface and, hence, the charge transport properties of devices such as GaSb-InAs nanowire TFETs. STEM-EELS thus represents a very promising technique for understanding nanowire physical properties, such as differing electrical behavior across the radial and axial heterointerfaces of GaSb-InAs nanowires for TFET applications.

Although zinc-blende (ZB) and wurtzite (WZ) structures differ only in the atomic stacking sequence, mixing of crystal phases can strongly affect the electronic properties, a problem particularly common to bottom up-grown nanostructures. A lack of understanding of the nature of electronic transport at crystal phase junctions thus severely limits our ability to develop functional nanowire devices. In this work we investigated electron transport in InAs nanowires with designed mixing of crystal structures, ZB/WZ/ZB, by temperature-dependent electrical measurements. The WZ inclusion gives rise to an energy barrier in the conduction band. Interpreting the experimental result in terms of thermionic emission and using a drift-diffusion model, we extracted values for the WZ/ZB band offset, 135 ± 10 meV, and interface sheet polarization charge density on the order of 10–3 C/m2. The extracted polarization charge density is 1–2 orders of magnitude smaller than previous experimental results, but in good agreement wit...

The opportunity to engineer III-V nanowires in wurtzite and zinc blende crystal structure allows for exploring properties not conventionally available in the bulk form as well as opening the opportunity for use of additional degrees of freedom in device fabrication. However, the fundamental understanding of the nature of polytypism in III-V nanowire growth is still lacking key ingredients to be able to connect the results of modeling and experiments. Here we show InP nanowires of both pure wurtzite and pure zinc blende grown simultaneously on the same InP [100]-oriented substrate. We find wurtzite nanowires to grow along [Formula: see text] and zinc blende counterparts along [Formula: see text]. Further, we discuss the nucleation, growth, and polytypism of our nanowires against the background of existing theory. Our results demonstrate, first, that the crystal growth conditions for wurtzite and zinc blende nanowire growth are not mutually exclusive and, second, that the interface energies predominantly determine the crystal structure of the nanowires.

Here we investigate the feasibility of silver as seed-particle material to synthesize GaAs nanowires and show that both crystal phase and growth direction can be controlled by choice of substrate orientation. A (111)B substrate orientation can be used to form vertically aligned wurtzite GaAs nanowires and a (100) substrate orientation to form vertically aligned zinc blende GaAs nanowires. A 45-50% yield of vertical nanowire growth is achieved on the (100) substrate orientation without employing any type of surface modification or nucleation strategy to promote a vertical growth direction. In addition, photoluminescence measurements reveal that the photon emission from the silver seeded wurtzite GaAs nanowires is characterized by a single and narrow emission peak at 1.52 eV.

Using AlSb as the model system, we demonstrate that kinetic limitations can lead to the preferential growth of wurtzite (WZ) AlSb shells rather than the thermodynamically stable zinc-blende (ZB) AlSb and that the WZ and ZB relative thickness can be tuned by a careful control of the deposition parameters. We report selective heteroepitaxial radial growth of AlSb deposited by metal-organic vapor phase epitaxy (MOVPE) on InAs nanowire core templates with engineered lengths of axial WZ and ZB segments. AlSb shell thickness, crystal phase, nanostructure, and composition are investigated as a function of the shell growth temperature, Ts, using scanning electron microscopy, transmission electron microscopy, electron tomography, and energy-dispersive X-ray spectroscopy. We find that ZB- and WZ-structured AlSb shells grow heteroepitaxially around the ZB and WZ segments of the InAs core, respectively. Surprisingly, at 390 < Ts < 450 °C, the WZ-AlSb shells are thicker than the ZB-AlSb shells, and their thickness inc...

We demonstrate the control of multiphoton electron excitations in InAs nanowires (NWs) by altering the crystal structure and the light polarization. Using few-cycle, near-infrared laser pulses from an optical parametric chirped-pulse amplification system, we induce multiphoton electron excitations in InAs nanowires with controlled wurtzite (WZ) and zincblende (ZB) segments. With a photoemission electron microscope, we show that we can selectively induce multiphoton electron emission from WZ or ZB segments of the same wire by varying the light polarization. Developing \textit{ab-initio GW} calculations of 1st to 3rd order multiphoton excitations and using finite-difference time-domain simulations, we explain the experimental findings: While the electric-field enhancement due to the semiconductor/vacuum interface has a similar effect for all NW segments, the 2nd and 3rd order multiphoton transitions in the band structure of WZ InAs are highly anisotropic, in contrast to ZB InAs. As the crystal phase of NWs can be precisely and reliably tailored, our findings opens up for new semiconductor optoelectronics with controllable nanoscale emission of electrons through vacuum or dielectric barriers., 6 figures, 27 pages (including cover picture)

We present a study of InAs/InSb heterostructured nanowires by X-ray photoemission spectroscopy (XPS), scanning tunneling microscopy (STM), and in-vacuum electrical measurements. Starting with pristine nanowires covered only by the native oxide formed through exposure to ambient air, we investigate the effect of atomic hydrogen cleaning on the surface chemistry and electrical performance. We find that clean and unreconstructed nanowire surfaces can be obtained simultaneously for both InSb and InAs by heating to 380 ± 20 °C under an H2 pressure 2 × 10(-6) mbar. Through electrical measurement of individual nanowires, we observe an increase in conductivity of 2 orders of magnitude by atomic hydrogen cleaning, which we relate through theoretical simulation to the contact-nanowire junction and nanowire surface Fermi level pinning. Our study demonstrates the significant potential of atomic hydrogen cleaning regarding device fabrication when high quality contacts or complete control of the surface structure is required. As hydrogen cleaning has recently been shown to work for many different types of III-V nanowires, our findings should be applicable far beyond the present materials system.

Polytype nanodots are arguably the simplest nanodots than can be made, but their technological control was, up to now, challenging. We have developed a technique to produce nanowires containing exactly one polytype nanodot in GaAs with thickness control. These nanodots have been investigated by photoluminescence, which has been cross-correlated with transmission electron microscopy. We find that short (4-20 nm) zincblende GaAs segments/dots in wurtzite GaAs confine electrons and that the inverse system confines holes. By varying the thickness of the nanodots we find strong quantum confinement effects which allows us to extract the effective mass of the carriers. The holes at the top of the valence band have an effective mass of approximately 0.45 m0 in wurtzite GaAs. The thinnest wurtzite nanodot corresponds to a twin plane in zincblende GaAs and gives efficient photoluminescence. It binds an exciton with a binding energy of roughly 50 meV, including central cell corrections.

Nanostructures have many material, electronic, and optical properties that are not found in bulk systems and that are relevant for technological applications. For example, nanowires realized from III-V semiconductors can be grown into a wurtzite crystal structure. This crystal structure does not naturally exist in bulk where these materials form the zinc-blende counterpart. Being able to concomitantly grow these nanowires in the zinc-blende and/or wurtzite crystal structure provides an important degree of control for the design and optimization of optoelectronic applications based on these semiconductor nanostructures. However, the refractive indices of this new crystallographic phase have so far not been elucidated. This shortcoming makes it impossible to predict and utilize the full potential of these new nanostructured materials for optoelectronics applications: a careful design and optimization of optical resonances by tuning the nanostructure geometry is needed to achieve optimal performance. Here, we report and analyze striking differences in the optical response of nanophotonic resonances in wurtzite and zinc-blende InAs nanowire arrays. Specifically, through reflectance measurements we find that the resonance can be tuned down to λ ≈ 380 nm in wurtzite nanowires by decreasing the nanowire diameter. In stark contrast, a similar tuning to below λ ≈ 500 nm is not possible in the zinc-blende nanowires. Furthermore, we find that the wurtzite nanowires can absorb twice as strongly as the zinc-blende nanowires. We attribute these strikingly large differences in resonant behavior to large differences between the refractive indices of the two crystallographic phases realized in these nanostructures. We anticipate our findings to be relevant for other III-V materials as well as for all material systems that manifest polytypism. Taken together, our results demonstrate crystal phase engineering as a potentially new design dimension for optoelectronics applications.

We report the observation of a thermoelectric power factor in InAs nanowires that exceeds that predicted by a single-band bulk model by up to an order of magnitude at temperatures below about 20 K. We attribute this enhancement effect not to the long-predicted 1D subband effects but to quantum-dot-like states that form in electrostatically nonuniform nanowires as a result of interference between propagating states and 0D resonances.

It is of contemporary interest to fabricate nanowires having quantum confinement and one-dimensional subband formation. This is due to a host of applications, for example, in optical devices, and in quantum optics. We have here fabricated and optically investigated narrow, down to 10 nm diameter, wurtzite GaAs nanowires which show strong quantum confinement and the formation of one-dimensional subbands. The fabrication was bottom up and in one step using the vapor-liquid-solid growth mechanism. Combining photoluminescence excitation spectroscopy with transmission electron microscopy on the same individual nanowires, we were able to extract the effective masses of the electrons in the two lowest conduction bands as well as the effective masses of the holes in the two highest valence bands. Our results, combined with earlier demonstrations of thin crystal phase nanodots in GaAs, set the stage for the fabrication of crystal phase quantum dots having full three-dimensional confinement.

We present electrical characterization of broken gap GaSb-InAsSb nanowire heterojunctions. Esaki diode characteristics with maximum reverse current of 1750 kA/cm(2) at 0.50 V, maximum peak current of 67 kA/cm(2) at 0.11 V, and peak-to-valley ratio (PVR) of 2.1 are obtained at room temperature. The reverse current density is comparable to that of state-of-the-art tunnel diodes based on heavily doped p-n junctions. However, the GaSb-InAsSb diodes investigated in this work do not rely on heavy doping, which permits studies of transport mechanisms in simple transistor structures processed with high-κ gate dielectrics and top-gates. Such processing results in devices with improved PVR (3.5) and stability of the electrical properties.

InAs/GaSb nanowire heterostructures with thin GaInAs inserts were grown by MOVPE and characterized by electrical measurements and transmission electron microscopy. Down-scaling of the insert thickness was limited because of an observed sensitivity of GaSb nanowire growth to the presence of In. By employing growth interrupts in between the InAs and GaInAs growth steps it was possible to reach an insert thickness down to 25 nm. Two-terminal devices show a diode behavior, where temperature-dependent measurements indicate a heterostructure barrier height of 0.5 eV, which is identified as the valence band offset between the InAs and GaSb. Three-terminal transistor structures with a top-gate positioned at the heterointerface show clear indications of band-to-band tunnelling.

We demonstrate here a method for controlled production of complex self-assembled three-dimensional networks of InAs nanowires on a substrate, based on sequentially seeded epitaxial nanowire structures, or "nanotrees". A position-controlled array of trunk nanowires is first produced using lithographically defined Au particles as seeds. With these wires positioned along the proper crystallographic directions with respect to each other, nanotree branches grow toward neighboring trunks, connecting them together. Finally, we investigate the crystal structure of the interconnected nanotrees, demonstrating that branch growth after the contact with the second trunk has an epitaxial relationship to that trunk.

The atomic distances in hexagonal polytypes of III-V compound semiconductors differ from the values expected from simply a change of the stacking sequence of (111) lattice planes. While these changes were difficult to quantify so far, we accurately determine the lattice parameters of zinc blende, wurtzite, and 4H polytypes for InAs and InSb nanowires, using X-ray diffraction and transmission electron microscopy. The results are compared to density functional theory calculations. Experiment and theory show that the occurrence of hexagonal bilayers tend to strech the distances of atomic layers parallel to the c-axis and to reduce the in-plane distances compared to those in zinc blende. The change of the lattice parameters scales linearly with the hexagonality of the polytype, defined as the fraction of bilayers with hexagonal character within one unit cell. Document Type: Article

The modified phonon dispersion is of importance for understanding the origin of the reduced heat conductivity in nanowires. We have measured the phonon dispersion for 50 nm diameter InSb (111) nanowires using time-resolved X-ray diffraction. By comparing the sound speed of the bulk (3880 m/s) and that of a classical thin rod (3600 m/s) to our measurement (2880 m/s), we conclude that the origin of the reduced sound speed and thereby to the reduced heat conductivity is that the C44 elastic constant is reduced by 35% compared to the bulk material.

Using scanning tunneling microscopy and spectroscopy we study the atomic scale geometry and electronic structure of GaAs nanowires exhibiting controlled axial stacking of wurtzite (Wz) and zinc blende (Zb) crystal segments. We find that the nonpolar low-index surfaces {110}, {101[overline]0}, and {112[overline]0} are unreconstructed, unpinned, and without states in the band gap region. Direct comparison between Wz and Zb GaAs reveal a type-II band alignment and a Wz GaAs band gap of 1.52 eV.

III-V-based nanowires usually exhibit random mixtures of wurtzite (WZ) and zinc blende (ZB) crystal structure, and pure crystal phase wires represent the exception rather than the rule. In this work, the effective group V hydride flow was the only growth parameter which was changed during MOVPE growth to promote transitions from WZ to ZB and from ZB to WZ. Our technique works in the same way for all investigated III-Vs (GaP, GaAs, InP, and InAs), with low group V flow for WZ and high group V flow for ZB conditions. This strongly suggests a common underlying mechanism. It displays to our best knowledge the simplest changes of the growth condition to control the nanowire crystal structure. The inherent reduction of growth variables is a crucial requirement for the interpretation in the frame of existing understanding of polytypism in III-V nanowires. We show that the change in surface energetics of the vapor-liquid-solid system at the vapor-liquid and liquid-solid interface is likely to control the crystal structure in our nanowires.

By combining in situ and ex situ transmission electron microscopy measurements, we examine the factors that control the morphology of “hybrid” nanowires that include group III–V and group IV materials. We focus on one materials pair, GaP/Si, for which we use a wide range of growth parameters. We show through video imaging that nanowire morphology depends on growth conditions, but that a general pattern emerges where either single kinks or inclined defects form some distance after the heterointerface. We show that pure Si nanowires can be made to exhibit the same kinks and defects by changing their droplet volume. From this we derive a model where droplet geometry drives growth morphology and discuss optimization strategies. We finally discuss morphology control for material pairs where the second material kinks immediately at the heterointerface and show that an interlayer between segments can enable the growth of unkinked hybrid nanowires.

The Ga(x)In(1-x)Sb ternary system has many interesting material properties, such as high carrier mobilities and a tunable range of bandgaps in the infrared. Here we present the first report on the growth and compositional control of Ga(x)In(1-x)Sb material grown in the form of nanowires from Au seeded nanoparticles by metalorganic vapor phase epitaxy. The composition of the grown Ga(x)In(1-x)Sb nanowires is precisely controlled by tuning the growth parameters where x varies from 1 to ∼0.3. Interestingly, the growth rate of the Ga(x)In(1-x)Sb nanowires increases with diameter, which we model based on the Gibbs-Thomson effect. Nanowire morphology can be tuned from high to very low aspect ratios, with perfect zinc blende crystal structure regardless of composition. Finally, electrical characterization on nanowire material with a composition of Ga(0.6)In(0.4)Sb showed clear p-type behavior.

We demonstrate two very different morphologies for GaP and GaAs nanowires grown by Au-assisted MOVPE on Si(111) substrates: rodlike wires and tapered wires with sharp tips. We show that the morphology is related to the stability of the particles at the wire tips during growth, and we propose that the mechanism of this effect is diffusion of Au away from the tip. Diffusion occurs, leading to tapered wires, only if there is a clean Si surface to act as a reservoir for the Au. Furthermore, the presence of indium in the particles, even at background levels from previous growth runs, inhibits the migration of Au. These results demonstrate a dramatic example of the sensitivity of wire morphology to substrate and particle chemistry, which could provide an important tool to tune nanowire morphology through particle alloying or surface treatment.

We present an extensive investigation of the epitaxial growth of Au-assisted axial heterostructure nanowires composed of group IV and III-V materials and derive a model to explain the overall morphology of such wires. By analogy with 2D epitaxial growth, this model relates the wire morphology (i.e., whether it is kinked or straight) to the relationship of the interface energies between the two materials and the particle. This model suggests that, for any pair of materials, it should be easier to form a straight wire with one interface direction than the other, and we demonstrate this for the material combinations presented here. However, such factors as kinetics and the use of surfactants may permit the growth of straight double heterostructure nanowires. Finally, we demonstrate that branched nanowire heterostructures, also known as nanotrees, can be successfully explained by the same model.

We report the temperature dependence of the Au-assisted growth of InAs nanowires in MOVPE. Extensive studies of the growth of such nanowires have attributed growth to the so-called vapor-liquid-solid (VLS) mechanism, with a liquid Au-In alloy particle. We assert here that growth is instead assisted by a solid particle and does not occur at all when the particle is a liquid. Thus the temperature range of InAs nanowire growth is limited by the melting of the Au-In alloy. Comparison with growth of InAs nanowires in the same system assisted by a layer of SiO(x) is used to support this conclusion.