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A review of models for determining the thermoelectric transport coefficients S (Seebeck coefficient), σ (electrical conductivity), and κ e (electronic thermal conductivity) is presented, for the cases of bulk and nanowire structures, along with derivations and a discussion of calculation methods. Results for the transport coefficients in GaAs, InAs, InP and InSb are used to determine the thermoelectric figure of merit, where an enhancement by two orders of magnitude is found for the nanowire case as compared with the bulk. The optimal electron concentration is determined as a function of nanowire diameter for both background and modulation doped nanowires.

GaAs nanowire (NW) arrays were grown by molecular beam epitaxy using the self-assisted vapor−liquid−solid method with Ga droplets as seed particles. A Ga pre-deposition step is examined to control NW yield and diameter. The NW yield can be increased with suitable duration of a Ga pre-deposition step but is highly dependent on oxide hole diameter and surface conditions. The NW diameter was determined by vapor-solid growth on the NW sidewalls, rather than Ga pre-deposition. The maximum NW yield with a Ga pre-deposition step was very close to 100%, established at shorter Ga deposition durations and for larger holes. This trend was explained within a model where maximum yield is obtained when the Ga droplet volume approximately equals the hole volume.

International audience; The droplet contact angle and morphology of the growth interface (vertical, tapered or truncated facets) are known to affect the zincblende (ZB) or wurtzite (WZ) crystal phase of III–V nanowires (NWs) grown by the vapor-liquid-solid method. Here, we present a model which describes the dynamics of the morphological evolution in self-catalyzed III–V NWs in terms of the time-dependent (or length-dependent) contact angle or top nanowire radius under varying material fluxes. The model fits quite well the contact angle dynamics obtained by in situ growth monitoring of self-catalyzed GaAs NWs in a transmission electron microscope. These results can be used for modeling the interface dynamics and the related crystal phase switching and for obtaining ZB-WZ heterostructures in III–V.

Numerical optimization has been used to determine the optimum junction design for core-shell nanowires used in betavoltaic generators. A genetic algorithm has been used to calculate the relative thickness, height, and doping of each segment within silicon, gallium arsenide, and gallium phosphide nanowires. Using the simulated spectra and energy deposition of nickel-63, nickel citrate, tritium, and tritiated butyl, devices with power output and overall efficiency up to 8 µW.cm-2 and 12%, respectively, have been predicted. Compared to previously investigated axial nanowires, the core-shell structures simulated here have realized drastic improvements by reducing surface recombination for longer nanowires. In addition, core-shell nanowires are shown to be capable of nearly matching the ideal performance predicted for this device structure. A new approach for calculating the practical upper limit of betavoltaic performance is presented and additional methods for improvement are discussed.

Semiconductor nanowires (NWs) are a candidate technology for future optoelectronic devices. One of the critical issues in NWs is the control of impurity doping for the formation of p-n junctions. In this study, beryllium (p-type dopant) and tellurium (n-type dopant) in self-assisted GaAs NWs was studied. The GaAs NWs were grown on (111) Si by molecular beam epitaxy using the self-assisted method. The dopant incorporation in the self-assisted GaAs NWs was investigated using Raman spectroscopy, photoluminescence, secondary ion mass spectrometry and electron holography. Be-doped NWs showed similar carrier concentration as compared to thin film (TF) standards. However, Te-doped NWs showed at least a one order of magnitude lower carrier concentration as compared to TF standards. Dopant incorporation mechanisms in NWs are discussed.

An analytical growth model is presented to explain the influence of antimony fractional flux on the morphology evolution of catalyst-free InAs1-x Sb x semiconductor nanowires grown by the selective-area vapor-solid mechanism on a Si (111) substrate by molecular beam epitaxy. Increasing Sb fractional flux promoted radial growth and suppressed axial growth, resulting in 'nano-disks'. This behavior is explained by a model of indium adatom diffusion along nanowire facets.

Gallium arsenide nanowires have shown considerable promise for use in applications in which the absorption of light is required. When the nanowires are oriented vertically, a considerable amount of light can be absorbed, leading to significant heating effects. Thus, it is important to understand the threshold power densities that vertical GaAs nanowires can support, and how the nanowire morphology is altered under these conditions. Here, resonant photo-thermal modification of vertical GaAs nanowires was studied using both Raman spectroscopy and electron microscopy techniques. Resonant waveguiding, and subsequent absorption of the excited optical mode reduces the irradiance vertical GaAs nanowires can support relative to horizontal ones, by three orders of magnitude before the onset of structural changes occur. A power density of only 20 W mm(-2) was sufficient to induce local heating in the nanowires, resulting in the formation of arsenic species. Upon further increasing the power, a hollow nanowire morphology was realized. These findings are pertinent to all optical applications and spectroscopic measurements involving vertically oriented GaAs nanowires. Understanding the optical absorption limitations, and the effects of exceeding these limitations will help improve the development of all III-V nanowire devices.

A betavoltaic device is reported that directly converts beta energy from a 63Ni radioisotope into electrical energy by impact ionization in a GaP nanowire array. The GaP nanowires are grown in a periodic array by molecular beam epitaxy on silicon using the self-assisted vapor–liquid–solid method. By growing GaP nanowires with large packing fraction and length on the order of the maximum beta range, the nanowires can efficiently capture the betas with high energy conversion efficiency while using inexpensive Si substrates. Monte Carlo simulations predict a betavoltaic efficiency in agreement with experimental results. The nanowire betavoltaic device can be used as a power source for nano-/micro-systems such as mobile electronic devices, implantable medical devices, and wireless sensor networks.

Patterned arrays of self-assisted GaP nanowires (NWs) were grown on a Si substrate by gas source molecular beam epitaxy using various V/III flux ratios from 1-6, and various pitches from 360-1000 nm. As the V/III flux ratio was increased from 1-6, the NWs showed a change in morphology from outward tapering to straight, and eventually to inward tapering. The morphologies of the self-assisted GaP NWs are well described by a simple kinetic equation for the NW radius versus the position along the NW axis. The most important growth parameter that governs the NW morphology is the V/III flux ratio. Sharpened NWs with a stable radius equal to only 12 nm at a V/III flux of 6 were achieved, demonstrating their suitability for the insertion of quantum dots.

We report the structural, optical and electrical properties of GaAs quantum dots (QDs) embedded along GaP nanowires. The GaP nanowires contained p-i-n junctions with 15 consecutively grown GaAs QDs within the intrinsic region. The nanowires were grown by molecular beam epitaxy using the self-assisted vapor-liquid-solid process. The crystal structure of the NWs alternated between twinned ZB and WZ as the composition along the NW alternated between the GaP barriers and the GaAs QDs, respectively, leading to a polytypic structure with a periodic modulation of the NW sidewall facets. Photodetector devices containing QDs showed absorption beyond the bandgap of GaP in comparison to nanowires without QDs. Voltage-dependent measurements suggested a field emission process of carriers from the QDs.

InP nanowires with InAsP quantum dots (QDs) were grown by molecular beam epitaxy on a Si (111) substrates. The structure of the InAsP QDs were studied using transmission electron microscopy, allowing the development of a model where QD growth occurs by group V desorption from the surrounding substrate surface. Micro-photoluminescence was performed at 10 K showing emission at 1.47–1.49 eV from the InP wurtzite structure, and various emission peaks between 0.93 and 1.33 eV attributed to the QDs. The emission was tuned by the QD composition. The effectiveness of an AlInP passivation shell was demonstrated via an improvement in the photoluminescence intensity. Spectrally-resolved photocurrent measurements at room temperature demonstrated infrared response due to absorption within the QDs. The absorption red-shifted with increasing As composition of the QD.

The absorptance in vertical nanowire (nw) arrays is a result of three optical phenomena: radial mode resonances, near-field evanescent wave coupling, and Fabry-Perot (F-P) modes. The contribution of these optical phenomena to GaAs, InP and InAs nw absorptance was simulated using the finite element method. The study compared the absorptance between finite and semi-infinite nw lengths with varying geometrical parameters, including the nw diameter, length and array period. Simulation results showed that the resonance peak wavelength of the HE11 and HE12 radial modes linearly red-shifted with increasing nw diameter. The absorptance and spectral width of the resonance peaks increased as the nw length increased, with an absorptance plateau for very long nws that depended on diameter and period. Near-field coupling between neighboring nws was observed to increase with decreasing period. The effect of F-P modes was more pronounced for shorter nws, with a significant enhancement of HE12 over HE11 absorptance. Engineering of nw arrays to take advantage of these optical phenomena for multi-spectral photodetector applications is discussed.

Vertically oriented and ordered GaAs nanowire arrays have been grown by the self-assisted mechanism using substrates prepared with nano-patterned oxide templates. Patterned Ga-assisted GaAs nanowire growth on (111) silicon by molecular beam epitaxy showed that the axial and radial growth rates increased with increasing interhole spacing. A model is described which accounts for the correlation of the final length and diameter with pattern pitch. The model considers that growth material is supplied by a secondary flux of both gallium and arsenic adatoms desorbing from the oxide surface between the nanowires which subsequently impinge on the liquid droplet and nanowire sidewalls. We show that shading of the incident and scattered flux by neighboring nanowires in the array can strongly affect the axial and radial growth rates, leading to significant differences in final nanowire morphologies.

Numerical simulation of the photocurrent density is performed for a two-junction nanowire (NW)-on-silicon solar cell under AM1.5G illumination. The photocurrent density is determined for NW diameters from 100?250?nm, period (spacing) from 250?1000?nm, and length of 5??m. The dependence of photocurrent density on NW bandgap is also determined. For each NW bandgap, the optimum diameter and period are determined to obtain current matching between the top NW cell and the bottom Si cell.

We describe methods of Ga droplet consumption in Ga-assisted GaAs nanowires, and their impact on the crystal structure at the tip of nanowires. Droplets are consumed under different group V flux conditions and the resulting tip crystal structure is examined by transmission electron microscopy. The use of GaAsP marker layers provides insight into the behavior of the Ga droplet during different droplet consumption conditions. Lower group V droplet supersaturations lead to a pure zincblende stacking-fault-free tip crystal structure, which improved the performance of a nanowire-based photovoltaic device.

A periodic array of vertical InSb nanowires (nws) was designed for photodetectors in the mid-wavelength infrared (MWIR) region (λ = 3-5 μm). Simulations, using the finite element method, were implemented to optimize the nw array geometrical parameters (diameter (D), period (P), and length (L)) for high optical absorptance, which exceeded that of a thin film of equal thickness. Our results showed HE1n resonances in InSb nw arrays can be tuned by adjusting D and P, thus enabling multispectral absorption throughout the near infrared to MWIR region. Optical absorptance was investigated for a practical photodetector consisting of a vertical InSb nw array embedded in bisbenzocyclobutene (BCB) as a support layer for an ultrathin Ni contact layer. Polarization sensitivity of the photodetector is examined.

Vertically aligned ZnO nanowires (NWs) were grown on Au-nanocluster-seeded amorphous SiO(2) films by the advective transport and deposition of Zn vapours obtained from the carbothermal reaction of graphite and ZnO powders. Both the NW volume and visible-to-UV photoluminescence ratio were found to be strong functions of, and hence could be tailored by, the (ZnO+C) source-SiO(2) substrate distance. We observe C flakes on the ZnO NWs/SiO(2) substrates which exhibit short NWs that developed on both sides. The SiO(2) and C substrates/NW interfaces were studied in detail to determine growth mechanisms. NWs on Au-seeded SiO(2) were promoted by a rough ZnO seed layer whose formation was catalysed by the Au clusters. In contrast, NWs grew without any seed on C. A correlation comprising three orders of magnitude between the visible-to-UV photoluminescence intensity ratio and the NW volume is found, which results from a characteristic Zn partial pressure profile that fixes both O deficiency defect concentration and growth rate.

This special issue of Nanotechnology focuses on studies illustrating the application of nanowires for energy including solar cells, efficient lighting and water splitting. Over the next three decades, nanotechnology will make significant contributions towards meeting the increased energy needs of the planet, now known as the TeraWatt challenge. Nanowires in particular are poised to contribute significantly in this development as presented in the review by Hiralal et al [1]. Nanowires exhibit light trapping properties that can act as a broadband anti-reflection coating to enhance the efficiency of solar cells. In this issue, Li et al [2] and Wang et al [3] present the optical properties of silicon nanowire and nanocone arrays. In addition to enhanced optical properties, core–shell nanowires also have the potential for efficient charge carrier collection across the nanowire diameter as presented in the contribution by Yu et al [4] for radial junction a-Si solar cells. Hybrid approaches that combine organic and inorganic materials also have potential for high efficiency photovoltaics. A Si-based hybrid solar cell is presented by Zhang et al [5] with a photoconversion efficiency of over 7%. The quintessential example of hybrid solar cells is the dye-sensitized solar cell (DSSC) where an organic absorber (dye) coats an inorganic material (typically a ZnO nanostructure). Herman et al [6] present a method of enhancing the efficiency of a DSSC by increasing the hetero-interfacial area with a unique hierarchical weeping willow ZnO structure. The increased surface area allows for higher dye loading, light harvesting, and reduced charge recombination through direct conduction along the ZnO branches. Another unique ZnO growth method is presented by Calestani et al [7] using a solution-free and catalyst-free approach by pulsed electron deposition (PED). Nanowires can also make more efficient use of electrical power. Light emitting diodes, for example, will eventually become the dominant lighting technology due to its superior electrical to optical conversion efficiency. A unique LED structure based on CdS is presented by Ye et al [8]. A detailed study by Nguyen et al [9] provides a fundamental understanding of the non-radiative recombination mechanisms in GaN-based white light emitting nanowire diodes grown on Si substrates. Another application of III-nitrides is in photovoltaic devices (solar cells) [10]. InGaN is the only semiconductor alloy whose energy bandgap can be continuously varied across nearly the entire solar spectrum, promising a new generation of solar cells. Another potentially important application for nanowires is the efficient production of H2 from the photocatalytic splitting of water, where the H2 can be used as an energy carrier. Water splitting based on unique nanostructures include Fe2O3 [11], CuS/ZnO [12], and ZnO/Si [13]. Another candidate for photocatalysis, among other applications, is copper oxide nanowires, reviewed by Gregor et al [14]. References [1] Hiralal P, Unalan H E and Amaratunga G A J 2012 Nanotechnology 23 194002 [2] Li J, Yu H and Li Y 2012 Nanotechnology 23 194010 [3] Wang B and Leu P W 2012 Nanotechnology 23 194003 [4] Yu L, O'Donnell B, Foldyna M, and Roca i Cabarrocas P 2012 Nanotechnology 23 194011 [5] Zhang F, Song T and Sun B 2012 Nanotechnology 23 194006 [6] Herman I, Yeo J, Hong S, Lee D, Nam K H, Choi J, Hong W, Lee D, Grigoropoulos C P and Ko S H 2012 Nanotechnology 23 194005 [7] Calestani D, Pattini F, Bissoli F, Gilioli E, Villani M and Zappettini A 2012 Nanotechnology 23 194008 [8] Ye Y, Yu B, Gao Z, Mang H, Zhang H, Dai L and Qin G 2012 Nanotechnology 23 194004 [9] Nguyen H P T, Djavid M, Cui K and Mi Z 2012 Nanotechnology 23 194012 [10] Wierer J J Jr, Li Q, Koleske D D, Lee S R L and Wang G T 2012 Nanotechnology 23 194007 [11] Chernomordik B D, Russell H B, Cvelbar U, Jasinski J B, Kumar V, Deutsch T and Sunkara M K 2012 Nanotechnology 23 194009 [12] Lee M and Yong K 2012 Nanotechnology 23 194014 [13] Sun K, Madsen K, Andersen P, Bao W, Sun Z and Wang D 2012 Nanotechnology 23 194013 [14] Gregor F and Cvelbar U 2012 Nanotechnology 23 194001

The morphology and crystal structure of Au-seeded GaAs nanowires (NWs) grown by molecular beam epitaxy were investigated as a function of the temperature, V/III flux ratio, and Ga flux. Low and intermediate growth temperatures of 400 and 500 °C resulted in a strongly tapered morphology, with stacking faults occurring at an average rate of 0.1 nm(-1). NWs with uniform diameter and the occurrence of crystal defects reduced by more than an order of magnitude were achieved at 600 °C, a V/III flux ratio of 2.3, and a Ga impingement rate on the surface of 0.07 nm s(-1). Comparison of nanowire densities on the various post-growth surfaces suggests a possible incubation time between the moment the Ga shutter is opened and when nanowire growth is initiated. Increasing the flux ratio favored uniform sidewall growth, making the process suitable for the fabrication of core-shell structures.

GaAs nanowire (NW)-based p-n photovoltaic devices, with two distinct p and n spatial distributions and where Te was the n-dopant, have been studied by impedance spectroscopy in the 10(3)-10(7) Hz frequency range and the - 1.5-1.5 V bias range. For a large n-core/p-shell overlap region within NWs in a coaxial geometry, the p-n junction properties (DC rectification and p-n depletion capacitance) are found to prevail. The impedance data at low bias for both NW devices show large frequency dispersions with relaxation frequencies that are compatible with carrier re-emission times from traps due to GaAs surface states. An increasing conductance with increasing frequency for low bias is observed, suggesting hopping transport through localized states. For large bias the conductance increases exponentially with bias and is frequency independent, indicating conduction through extended states in this regime.

An experimental approach to achieving phase purity in nanowires through molecular beam epitaxy growth is presented. Superlattice heterostructured nanowires were grown, consisting of alternating layers of GaAsP and GaP. The observed core-multishell heterostructure, extending axially and radially, is attributed to simultaneous Au-assisted vertical growth and diffusion-limited radial growth along lateral nanowire facets. Growth interruptions at the GaAsP/GaP interfaces allowed for the elimination of stacking faults and the growth of nanowires with a single-crystalline wurtzite phase.

Experimental data and a model are presented which define the boundary values of V/III flux ratio and growth temperature for droplet-assisted nucleation of InAs semiconductor nanowires in selective-area epitaxy on SiO(x)/Si (111) substrates by molecular beam epitaxy. Within these boundaries, the substrate receives a balanced flux of group III and V materials allowing the growth of vertically oriented nanowires as compared to the formation of droplets or crystallites.

We report fabrication methods, including metal masks and dry etching, and demonstrate highly ordered vertical gallium arsenide nanowire arrays. The etching process created high aspect ratio, vertical nanowires with insignificant undercutting from the mask, allowing us to vary the diameter from 30 nm to 400 nm with a pitch from 250 nm to 1100 nm and length up to 2.2 μm. A diameter to pitch ratio of ∼68% was achieved. We also measured the reflectance from the nanowire arrays and show experimentally diameter-dependent strong absorption peaks resulting from resonant optical mode excitations within these nanowires. The reflectance curves match very well with simulations. The work done here paves the way towards achieving high efficiency solar cells and tunable photodetectors using III-V nanowires.

Dynamic and time-of-flight (TOF) secondary ion mass spectrometry (SIMS) was performed on vertically standing III-V nanowire ensembles embedded in Cyclotene polymer. By embedding the NWs in Cyclotene, the top surface of the sample was made planar, while the space between the NWs was filled to protect the background substrate from the ion beam, thus allowing for the NWs to be sputtered and analyzed evenly as a function of depth. Using thin film standards, SIMS analysis was used to calculate the impurity dopant concentration as a function of height in the NW ensemble. This marked the first use of conventional SIMS to accurately determine the doping density with excellent depth resolution. Additionally, this is the first presentation of SIMS as the only reported tool for characterizing the segment height uniformity of any arbitrary axial heterostructure NW ensemble.

The viability of four organic polymers (S1808, SC200, SU8 and Cyclotene) as filling materials to achieve planarization of ensemble nanowire arrays is reported. Analysis of the porosity, surface roughness and thermal stability of each filling material was performed. Sonication was used as an effective method to remove the tops of the nanowires (NWs) to achieve complete planarization. Ensemble nanowire devices were fully fabricated and I-V measurements confirmed that Cyclotene effectively planarizes the NWs while still serving the role as an insulating layer between the top and bottom contacts. These processes and analysis can be easily implemented into future characterization and fabrication of ensemble NWs for optoelectronic device applications.

The effect of sulfur passivation on core-shell p-n junction GaAs nanowire (NW) solar cells has been investigated. Devices of two types were investigated, consisting of indium tin oxide contact dots or opaque Au finger electrodes. Lateral carrier transport from the NWs to the contact fingers was achieved via a p-doped GaAs surface conduction layer. NWs between the opaque contact fingers had sidewall surfaces exposed for passivation by sulfur. The relative cell efficiency increased by 19% upon passivation. The contribution of the thin film grown between the NWs to the total cell efficiency was estimated by removing the NWs using a sonication procedure. Mechanisms of carrier transport and photovoltaic effects are discussed on the basis of spatially resolved laser scanning measurements.

InGaP nanowires (NWs) were grown by the Au-assisted method in a gas source molecular beam epitaxy system. The dependence of InGaP composition, morphology and stacking fault density was studied with respect to group III and V impingement rate and size of the Au particle. Compositional analysis showed that the NWs had an In-rich core and a Ga-rich shell structure. The In incorporation within the NW became limited as the Au seed particle size diminished or the group III and V flux decreased. The NWs had wurtzite (WZ) crystal structure with zinc blende (ZB) segments (stacking faults). The density of the stacking faults decreased as the group III flux decreased and the group V flux increased.

This paper reviews recent advances in engineering spin quantum bits (qubits) in semiconductor quantum dots and describes an approach based on top-gated semiconductor nanowire devices. Fast electrical single-spin manipulation is achievable, in principle, using the spin-orbit interaction intrinsic to III-V materials, such as InAs, in concert with AC electric fields. Combined with sub-nanosecond gate control of the nearest-neighbor exchange interaction and spin readout by spin-to-charge conversion, a fully electrical solid-state quantum processor is within reach. We outline strategies for spin manipulation, robust readout and mitigation of decoherence due to nuclear fields that, when combined in a single device, should give a viable multi-qubit testbed and a building block for larger scale quantum devices.

A detailed continuum model is presented for predicting the growth characteristics of GaAs nanowires during chemical beam epitaxy. The model describes the transport processes of Ga and As adatoms on the substrate and nanowire sidewalls, and through the nanoparticle and the nanowire-catalyst interface (NCI). The growth mechanisms of nanowires within the NCI are described using an extended step-flow kinetic model. The vapor-liquid-solid and vapor-solid-solid growth mechanisms are both described in the kinetic model. The growth rate of the nanowires, the surface and bulk concentrations of adatoms, and the role of transport processes of Ga and As adatoms during chemical beam epitaxy were investigated. The growth mechanisms of the nanowires were found to vary with increasing length of the nanowire.

Hybrid solar cells with an energy conversion efficiency of 1.04% were fabricated by spin-coating poly(3-hexylthiophene) (P3HT) polymer onto vertically aligned n-type GaAs nanowire arrays synthesized by molecular beam epitaxy. Experimental parameters such as the P3HT solvent mixing ratio of chlorobenzene to dichlorobenzene and nanowire surface etching were studied with a view to improving the energy conversion efficiency.

The influence of GaAs(100) substrate surface preparation on Au-catalysed GaAs nanowires was studied. Elongated pits of varying dimensions and orientation were formed on GaAs(100) substrates depending on the interaction with Au and surface oxides. The resulting surface topography is shown to influence the density and orientation of nanowires. [111] B-oriented nanowires nucleated from Au particles lying on the sidewall facets of the pits, while [011]-oriented nanowires nucleated from Au particles lying outside the pits.

GaP/GaAsP/GaP segmented nanowires were grown by gas source molecular beam epitaxy on silicon (111) substrates. The nanowires were grown by the vapour?liquid?solid process using Au nanoparticles. Transmission electron microscopy and energy dispersive x-ray spectroscopy indicated that the wires had wurtzite crystal structure with a core?multishell heterostructure. Stacking faults along the wire were removed after the growth-interrupted interfaces, indicating the potential for defect-free nanowires.