Vapor Phase Growth of Semiconductor Nanowires: Key Developments and Open Questions.

Nanowires are filamentary crystals with a tailored diameter that can be obtained using a plethora of different synthesis techniques. In this review, we focus on the vapor phase, highlighting the most influential achievements along with a historical perspective. Starting with the discovery of VLS, we feature the variety of structures and materials that can be synthesized in the nanowire form. We then move on to establish distinct features such as the three-dimensional heterostructure/doping design and polytypism. We summarize the status quo of the growth mechanisms, recently confirmed by in situ electron microscopy experiments and defining common ground between the different synthesis techniques. We then propose a selection of remaining defects, starting from what we know and going toward what is still to be learned. We believe this review will serve as a reference for neophytes but also as an insight for experts in an effort to bring open questions under a new light.

In situ passivation of GaAsSb nanowires for enhanced infrared photoresponse.

Surface passivation of semiconductor nanowires (NWs) is important for their optoelectronic properties and applications. Here, the in situ passivation effect of an epitaxial InP shell and the corresponding photodetector performance is experimentally studied. Compared with the unpassivated GaAs1- x Sb x core-only NWs, the GaAs1- x Sb x /InP core/shell NWs have shown much stronger photoluminescence and cathodoluminescence intensities. Correspondingly, the fabricated single GaAs1- x Sb x /InP core/shell NW photodetector shows a responsivity of 325.1 A W-1 (@ 1.3 µm and 1.5 V) that is significantly enhanced compared to that of single GaAs1- x Sb x core-only NW photodetectors (143.5 A W-1), with a comparable detectivity of 4.7 × 1010 and 5.3 × 1010 cm√Hz/W, respectively. This is ascribed to the enhanced carrier mobility and carrier concentration by the in situ passivation, which lead to both higher photoconductivity and dark-conductivity. Our results show that in situ passivation is an effective approach for performance enhancement of GaAs1-x Sb x NW based optoelectronic devices.

The Role of Polarity in Nonplanar Semiconductor Nanostructures.

The lack of mirror symmetry in binary semiconductor compounds turns them into polar materials, where two opposite orientations of the same crystallographic direction are possible. Interestingly, their physical properties (e.g., electronic or photonic) and morphological features (e.g., shape, growth direction, and so forth) also strongly depend on the polarity. It has been observed that nanoscale materials tend to grow with a specific polarity, which can eventually be reversed for very specific growth conditions. In addition, polar-directed growth affects the defect density and topology and might induce eventually the formation of undesirable polarity inversion domains in the nanostructure, which in turn will affect the photonic and electronic final device performance. Here, we present a review on the polarity-driven growth mechanism at the nanoscale, combining our latest investigation with an overview of the available literature highlighting suitable future possibilities of polarity engineering of semiconductor nanostructures. The present study has been extended over a wide range of semiconductor compounds, covering the most commonly synthesized III-V (GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb) and II-VI (ZnO, ZnTe, CdS, CdSe, CdTe) nanowires and other free-standing nanostructures (tripods, tetrapods, belts, and membranes). This systematic study allowed us to explore the parameters that may induce polarity-dependent and polarity-driven growth mechanisms, as well as the polarity-related consequences on the physical properties of the nanostructures.

Ballistic InSb Nanowires and Networks via Metal-Sown Selective Area Growth.

Selective area growth is a promising technique to realize semiconductor-superconductor hybrid nanowire networks, potentially hosting topologically protected Majorana-based qubits. In some cases, however, such as the molecular beam epitaxy of InSb on InP or GaAs substrates, nucleation and selective growth conditions do not necessarily overlap. To overcome this challenge, we propose a metal-sown selective area growth (MS SAG) technique, which allows decoupling selective deposition and nucleation growth conditions by temporarily isolating these stages. It consists of three steps: (i) selective deposition of In droplets only inside the mask openings at relatively high temperatures favoring selectivity, (ii) nucleation of InSb under Sb flux from In droplets, which act as a reservoir of group III adatoms, done at relatively low temperatures, favoring nucleation of InSb, and (iii) homoepitaxy of InSb on top of the formed nucleation layer under a simultaneous supply of In and Sb fluxes at conditions favoring selectivity and high crystal quality. We demonstrate that complex InSb nanowire networks of high crystal and electrical quality can be achieved this way. We extract mobility values of 10 000-25 000 cm2 V-1 s-1 consistently from field-effect and Hall mobility measurements across single nanowire segments as well as wires with junctions. Moreover, we demonstrate ballistic transport in a 440 nm long channel in a single nanowire under a magnetic field below 1 T. We also extract a phase-coherent length of ∼8 µm at 50 mK in mesoscopic rings.

Selectivity Map for Molecular Beam Epitaxy of Advanced III-V Quantum Nanowire Networks.

Selective-area growth is a promising technique for enabling of the fabrication of the scalable III-V nanowire networks required to test proposals for Majorana-based quantum computing devices. However, the contours of the growth parameter window resulting in selective growth remain undefined. Herein, we present a set of experimental techniques that unambiguously establish the parameter space window resulting in selective III-V nanowire networks growth by molecular beam epitaxy. Selectivity maps are constructed for both GaAs and InAs compounds based on in situ characterization of growth kinetics on GaAs(001) substrates, where the difference in group III adatom desorption rates between the III-V surface and the amorphous mask area is identified as the primary mechanism governing selectivity. The broad applicability of this method is demonstrated by the successful realization of high-quality InAs and GaAs nanowire networks on GaAs, InP, and InAs substrates of both (001) and (111)B orientations as well as homoepitaxial InSb nanowire networks. Finally, phase coherence in Aharonov-Bohm ring experiments validates the potential of these crystals for nanoelectronics and quantum transport applications. This work should enable faster and better nanoscale crystal engineering over a range of compound semiconductors for improved device performance.

Importance of point defect reactions for the atomic-scale roughness of III-V nanowire sidewalls.

The surface morphology of III-V semiconductor nanowires (NWs) protected by an arsenic cap and subsequently evaporated in ultrahigh vacuum is investigated with scanning tunneling microscopy and scanning transmission electron microscopy. We show that the changes of the surface morphology as a function of the NW composition and the nature of the seed particles are intimately related to the formation and reaction of surface point defects. Langmuir evaporation close to the congruent evaporation temperature causes the formation of vacancies which nucleate and form vacancy islands on {110} sidewalls of self-catalyzed InAs NWs. However, for annealing temperatures much smaller than the congruent temperature, a new phenomenon occurs: group III vacancies form and are filled by excess As atoms, leading to surface AsGa antisites. The resulting Ga adatoms nucleate with excess As atoms at the NW edges, producing monoatomic-step islands on the {110} sidewalls of GaAs NWs. Finally, when gold atoms diffuse from the seed particle onto the {110} sidewalls during evaporation of the protective As cap, Langmuir evaporation does not take place, leaving the sidewalls of InAsSb NWs atomically flat.

Twin-Induced InSb Nanosails: A Convenient High Mobility Quantum System.

Ultra narrow bandgap III-V semiconductor nanomaterials provide a unique platform for realizing advanced nanoelectronics, thermoelectrics, infrared photodetection, and quantum transport physics. In this work we employ molecular beam epitaxy to synthesize novel nanosheet-like InSb nanostructures exhibiting superior electronic performance. Through careful morphological and crystallographic characterization we show how this unique geometry is the result of a single twinning event in an otherwise pure zinc blende structure. Four-terminal electrical measurements performed in both the Hall and van der Pauw configurations reveal a room temperature electron mobility greater than 12,000 cm(2)·V(-1)·s(-1). Quantized conductance in a quantum point contact processed with a split-gate configuration is also demonstrated. We thus introduce InSb "nanosails" as a versatile and convenient platform for realizing new device and physics experiments with a strong interplay between electronic and spin degrees of freedom.

Simultaneous Selective-Area and Vapor-Liquid-Solid Growth of InP Nanowire Arrays.

Selective-area epitaxy is highly successful in producing application-ready size-homogeneous arrays of III-V nanowires without the need to use metal catalysts. Previous works have demonstrated excellent control of nanowire properties but the growth mechanisms remain rather unclear. Herein, we report a detailed growth study revealing that fundamental growth mechanisms of pure wurtzite InP ⟨111⟩A nanowires can indeed differ significantly from the simple picture of a facet-limited selective-area growth process. A dual growth regime with and without metallic droplet is found to coexist under the same growth conditions for different diameter nanowires. Incubation times and highly nonmonotonous growth rate behaviors are revealed and explained within a dedicated kinetic model.

Zn3As2 nanowires and nanoplatelets: highly efficient infrared emission and photodetection by an earth abundant material.

The development of earth abundant materials for optoelectronics and photovoltaics promises improvements in sustainability and scalability. Recent studies have further demonstrated enhanced material efficiency through the superior light management of novel nanoscale geometries such as the nanowire. Here we show that an industry standard epitaxy technique can be used to fabricate high quality II-V nanowires (1D) and nanoplatelets (2D) of the earth abundant semiconductor Zn3As2. We go on to establish the optoelectronic potential of this material by demonstrating efficient photoemission and detection at 1.0 eV, an energy which is significant to the fields of both photovoltaics and optical telecommunications. Through dynamical spectroscopy this superior performance is found to arise from a low rate of surface recombination combined with a high rate of radiative recombination. These results introduce nanostructured Zn3As2 as a high quality optoelectronic material ready for device exploration.

Room temperature GaAsSb single nanowire infrared photodetectors.

Antimonide-based ternary III-V nanowires (NWs) allow for a tunable bandgap over a wide range, which is highly interesting for optoelectronics applications, and in particular for infrared photodetection. Here we demonstrate room temperature operation of GaAs0.56Sb0.44 NW infrared photodetectors grown by metal organic vapor phase epitaxy. These GaAs0.56Sb0.44 NWs have uniform axial composition and show p-type conductivity with a peak field-effect mobility of ∼12 cm(2) V(-1) s(-1)). Under light illumination, single GaAs0.56Sb0.44 NW photodetectors exhibited typical photoconductor behavior with an increased photocurrent observed with the increase of temperature owing to thermal activation of carrier trap states. A broadband infrared photoresponse with a long wavelength cutoff at ∼1.66 µm was obtained at room temperature. At a low operating bias voltage of 0.15 V a responsivity of 2.37 (1.44) A/W with corresponding detectivity of 1.08 × 10(9) (6.55 × 10(8)) cm√Hz/W were achieved at the wavelength of 1.3 (1.55) µm, indicating that ternary GaAs0.56Sb0.44 NWs are promising photodetector candidates for small footprint integrated optical telecommunication systems.

In(x)Ga(1-x)As nanowires with uniform composition, pure wurtzite crystal phase and taper-free morphology.

Obtaining compositional homogeneity without compromising morphological or structural quality is one of the biggest challenges in growing ternary alloy compound semiconductor nanowires. Here we report growth of Au-seeded InxGa1-xAs nanowires via metal-organic vapour phase epitaxy with uniform composition, morphology and pure wurtzite (WZ) crystal phase by carefully optimizing growth temperature and V/III ratio. We find that high growth temperatures allow the InxGa1-xAs composition to be more uniform by suppressing the formation of typically observed spontaneous In-rich shells. A low V/III ratio results in the growth of pure WZ phase InxGa1-xAs nanowires with uniform composition and morphology while a high V/III ratio allows pure zinc-blende (ZB) phase to form. Ga incorporation is found to be dependent on the crystal phase favouring higher Ga concentration in ZB phase compared to the WZ phase. Tapering is also found to be more prominent in defective nanowires hence it is critical to maintain the highest crystal structure purity in order to minimize tapering and inhomogeneity. The InP capped pure WZ In0.65Ga0.35As core-shell nanowire heterostructures show 1.54 µm photoluminescence, close to the technologically important optical fibre telecommunication wavelength, which is promising for application in photodetectors and nanoscale lasers.

Atomic scale strain relaxation in axial semiconductor III-V nanowire heterostructures.

Combination of mismatched materials in semiconductor nanowire heterostructures offers a freedom of bandstructure engineering that is impossible in standard planar epitaxy. Nevertheless, the presence of strain and structural defects directly control the optoelectronic properties of these nanomaterials. Understanding with atomic accuracy how mismatched heterostructures release or accommodate strain, therefore, is highly desirable. By using atomic resolution high angle annular dark field scanning transmission electron microscopy combined with geometrical phase analyses and computer simulations, we are able to establish the relaxation mechanisms (including both elastic and plastic deformations) to release the mismatch strain in axial nanowire heterostructures. Formation of misfit dislocations, diffusion of atomic species, polarity transfer, and induced structural transformations are studied with atomic resolution at the intermediate ternary interfaces. Two nanowire heterostructure systems with promising applications (InAs/InSb and GaAs/GaSb) have been selected as key examples.

Gold-free ternary III-V antimonide nanowire arrays on silicon: twin-free down to the first bilayer.

With the continued maturation of III-V nanowire research, expectations of material quality should be concomitantly raised. Ideally, III-V nanowires integrated on silicon should be entirely free of extended planar defects such as twins, stacking faults, or polytypism, position-controlled for convenient device processing, and gold-free for compatibility with standard complementary metal-oxide-semiconductor (CMOS) processing tools. Here we demonstrate large area vertical GaAsxSb1-x nanowire arrays grown on silicon (111) by molecular beam epitaxy. The nanowires' complex faceting, pure zinc blende crystal structure, and composition are mapped using characterization techniques both at the nanoscale and in large-area ensembles. We prove unambiguously that these gold-free nanowires are entirely twin-free down to the first bilayer and reveal their three-dimensional composition evolution, paving the way for novel infrared devices integrated directly on the cost-effective Si platform.

Selective-area epitaxy of pure wurtzite InP nanowires: high quantum efficiency and room-temperature lasing.

We report the growth of stacking-fault-free and taper-free wurtzite InP nanowires with diameters ranging from 80 to 600 nm using selective-area metal-organic vapor-phase epitaxy and experimentally determine a quantum efficiency of ∼50%, which is on par with InP epilayers. We also demonstrate room-temperature, photonic mode lasing from these nanowires. Their excellent structural and optical quality opens up new possibilities for both fundamental quantum optics and optoelectronic devices.

Magnetotransport subband spectroscopy in InAs nanowires.

We report on magnetotransport measurements in InAs nanowires under a large magnetic field (up to 55 T), providing a spectroscopy of the one-dimensional electronic band structure. Large modulations of the conductance mediated by a control of the Fermi energy reveal the Landau fragmentation, carrying the fingerprints of the confined InAs material. Our numerical simulations of the magnetic band structure consistently support the experimental results and reveal key parameters of the electronic confinement.

Raman spectroscopy of self-catalyzed GaAs(1-x)Sb(x) nanowires grown on silicon.

Thanks to their wide band structure tunability, GaAs(1-x)Sb(x) nanowires provide exciting perspectives in optoelectronic and energy harvesting applications. The control of composition and strain of these ternary alloys is crucial in the determination of their optical and electronic properties. Raman scattering provides information on the vibrational properties of materials, which can be related to the composition and strain. We present a systematic study of the vibrational properties of GaAs(1-x)Sb(x) nanowires for Sb contents from 0 to 44%, as determined by energy-dispersive x-ray analyses. We find that optical phonons red-shift with increasing Sb content. We explain the shift by alloying effects, including mass disorder, dielectric changes and ionic plasmon coupling. The influence of Sb on the surface optical modes is addressed. Finally, we compare the luminescence yield between GaAs and GaAs(1-x)Sb(x), which can be related to a lower surface recombination rate. This work provides a reference for the study of ternary alloys in the form of nanowires, and demonstrates the tunability and high material quality of gold-free ternary antimonide nanowires directly grown on silicon.

Persistent enhancement of the carrier density in electron irradiated InAs nanowires.

We report a significant and persistent enhancement of the conductivity in free-standing non-intentionally doped InAs nanowires upon irradiation in ultra-high vacuum. Combining four-point probe transport measurements performed on nanowires with different surface chemistries, field effect based measurements and numerical simulations of the electron density, the change in the conductivity is found to be caused by an increase in the surface free carrier concentration. Although an electron beam of a few keV, typically used for the inspection and the processing of materials, propagates through the entire nanowire cross-section, we demonstrate that the electrical properties of the nanowire are predominantly affected by radiation-induced defects occurring at the nanowire surface and not in the bulk.

Demonstration of defect-free and composition tunable GaxIn1-xSb 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.

Faceting, composition and crystal phase evolution in III-V antimonide nanowire heterostructures revealed by combining microscopy techniques.

III-V antimonide nanowires are among the most interesting semiconductors for transport physics, nanoelectronics and long-wavelength optoelectronic devices due to their optimal material properties. In order to investigate their complex crystal structure evolution, faceting and composition, we report a combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM) study of gold-nucleated ternary InAs/InAs(1-x)Sb(x) nanowire heterostructures grown by molecular beam epitaxy. SEM showed the general morphology and faceting, TEM revealed the internal crystal structure and ternary compositions, while STM was successfully applied to characterize the oxide-free nanowire sidewalls, in terms of nanofaceting morphology, atomic structure and surface composition. The complementary use of these techniques allows for correlation of the morphological and structural properties of the nanowires with the amount of Sb incorporated during growth. The addition of even a minute amount of Sb to InAs changes the crystal structure from perfect wurtzite to perfect zinc blende, via intermediate stacking fault and pseudo-periodic twinning regimes. Moreover, the addition of Sb during the axial growth of InAs/InAs(1-x)Sb(x) heterostructure nanowires causes a significant conformal lateral overgrowth on both segments, leading to the spontaneous formation of a core-shell structure, with an Sb-rich shell.