Improving Quantum Well Tube Homogeneity Using Strained Nanowire Heterostructures.

Bottom-up grown nanostructures often suffer from significant dimensional inhomogeneity, and for quantum confined heterostructures, this can lead to a corresponding large variation in electronic properties. A high-throughput characterization methodology is applied to >15,000 nanoskived sections of highly strained GaAsP/GaAs radial core/shell quantum well heterostructures revealing high emission uniformity. While scanning electron microscopy shows a wide nanowire diameter spread of 540-60+60 nm, photoluminescence reveals a tightly bounded band-to-band transition energy of 1546-3+4 meV. A highly strained core/shell nanowire design is shown to reduce the dependence of emission on the quantum well width variation significantly more than in the unstrained case.

Long-Term Stability and Optoelectronic Performance Enhancement of InAsP Nanowires with an Ultrathin InP Passivation Layer.

The influence of nanowire (NW) surface states increases rapidly with the reduction of diameter and hence severely degrades the optoelectronic performance of narrow-diameter NWs. Surface passivation is therefore critical, but it is challenging to achieve long-term effective passivation without significantly affecting other qualities. Here, we demonstrate that an ultrathin InP passivation layer of 2-3 nm can effectively solve these challenges. For InAsP nanowires with small diameters of 30-40 nm, the ultrathin passivation layer reduces the surface recombination velocity by at least 70% and increases the charge carrier lifetime by a factor of 3. These improvements are maintained even after storing the samples in ambient atmosphere for over 3 years. This passivation also greatly improves the performance thermal tolerance of these thin NWs and extends their operating temperature from <150 K to room temperature. This study provides a new route toward high-performance room-temperature narrow-diameter NW devices with long-term stability.

Thermally-driven formation method for growing (quantum) dots on sidewalls of self-catalysed thin nanowires.

Embedding quantum dots (QDs) on nanowire (NW) sidewalls allows the integration of multi-layers of QDs into the active region of radial p-i-n junctions to greatly enhance light emission/absorption. However, the surface curvature makes the growth much more challenging compared with growths on thin-films, particularly on NWs with small diameters (Ø < 100 nm). Moreover, the {110} sidewall facets of self-catalyzed NWs favor two-dimensional growth, with the realization of three-dimensional Stranski-Krastanow growth becoming extremely challenging. Here, we have developed a novel thermally-driven QD growth method. The QD formation is driven by the system energy minimization when the pseudomorphic shell layer (made of QD material) is annealed under high-temperature, and thus without any restriction on the NW diameter or the participation of elastic strain. It has demonstrated that the lattice-matched Ge dots can be grown defect-freely in a controllable way on the sidewall facets of the thin (∼50 nm) self-catalyzed GaAs NWs without using any surfactant or surface treatment. This method opens a new avenue to integrate QDs on NWs, and can allow the formation of QDs in a wider range of materials systems where the growth by traditional mechanisms is not possible, with benefits for novel NWQD-based optoelectronic devices.

Self-Catalyzed AlGaAs Nanowires and AlGaAs/GaAs Nanowire-Quantum Dots on Si Substrates.

Self-catalyzed AlGaAs nanowires (NWs) and NWs with a GaAs quantum dot (QD) were monolithically grown on Si(111) substrates via solid-source molecular beam epitaxy. This growth technique is advantageous in comparison to the previously employed Au-catalyzed approach, as it removes Au contamination issues and renders the structures compatible with complementary metal-oxide-semiconductor (CMOS) technology applications. Structural studies reveal the self-formation of an Al-rich AlGaAs shell, thicker at the NW base and thinning towards the tip, with the opposite behavior observed for the NW core. Wide alloy fluctuations in the shell region are also noticed. AlGaAs NW structures with nominal Al contents of 10, 20, and 30% have strong room temperature photoluminescence, with emission in the range of 1.50-1.72 eV. Individual NWs with an embedded 4.9 nm-thick GaAs region exhibit clear QD behavior, with spatially localized emission, both exciton and biexciton recombination lines, and an exciton line width of 490 µeV at low temperature. Our results demonstrate the properties and behavior of the AlGaAs NWs and AlGaAs/GaAs NWQDs grown via the self-catalyzed approach for the first time and exhibit their potential for a range of novel applications, including nanolasers and single-photon sources.

Defect-Free Axially Stacked GaAs/GaAsP Nanowire Quantum Dots with Strong Carrier Confinement.

Axially stacked quantum dots (QDs) in nanowires (NWs) have important applications in nanoscale quantum devices and lasers. However, there is lack of study of defect-free growth and structure optimization using the Au-free growth mode. We report a detailed study of self-catalyzed GaAsP NWs containing defect-free axial GaAs QDs (NWQDs). Sharp interfaces (1.8-3.6 nm) allow closely stack QDs with very similar structural properties. High structural quality is maintained when up to 50 GaAs QDs are placed in a single NW. The QDs maintain an emission line width of <10 meV at 140 K (comparable to the best III-V QDs, including nitrides) after having been stored in an ambient atmosphere for over 6 months and exhibit deep carrier confinement (∼90 meV) and the largest reported exciton-biexciton splitting (∼11 meV) for non-nitride III-V NWQDs. Our study provides a solid foundation to build high-performance axially stacked NWQD devices that are compatible with CMOS technologies.

Robust Protection of III-V Nanowires in Water Splitting by a Thin Compact TiO2 Layer.

Narrow-band-gap III-V semiconductor nanowires (NWs) with a suitable band structure and strong light-trapping ability are ideal for high-efficiency low-cost solar water-splitting systems. However, due to their nanoscale dimension, they suffer more severe corrosion by the electrolyte solution than the thin-film counterparts. Thus, short-term durability is the major obstacle for using these NWs for practical water-splitting applications. Here, we demonstrated for the first time that a thin layer (∼7 nm thick) of compact TiO2 deposited by atomic layer deposition can provide robust protection to III-V NWs. The protected GaAs NWs maintain 91.4% of its photoluminescence intensity after 14 months of storage in ambient atmosphere, which suggests the TiO2 layer is pinhole-free. Working as a photocathode for water splitting, they exhibited a 45% larger photocurrent density compared with unprotected counterparts and a high Faraday efficiency of 91% and can also maintain a record-long highly stable performance among narrow-band-gap III-V NW photoelectrodes; after 67 h photoelectrochemical stability test reaction in a strong acid electrolyte solution (pH = 1), they show no apparent indication of corrosion, which is in stark contrast to the unprotected NWs that fully failed after 35 h. These findings provide an effective way to enhance both stability and performance of III-V NW-based photoelectrodes, which are highly important for practical applications in solar-energy-based water-splitting systems.

Fully in situ Nb/InAs-nanowire Josephson junctions by selective-area growth and shadow evaporation.

Josephson junctions based on InAs semiconducting nanowires and Nb superconducting electrodes are fabricated in situ by a special shadow evaporation scheme for the superconductor electrode. Compared to other metallic superconductors such as Al, Nb has the advantage of a larger superconducting gap which allows operation at higher temperatures and magnetic fields. Our junctions are fabricated by shadow evaporation of Nb on pairs of InAs nanowires grown selectively on two adjacent tilted Si (111) facets and crossing each other at a small distance. The upper wire relative to the deposition source acts as a shadow mask determining the gap of the superconducting electrodes on the lower nanowire. Electron microscopy measurements show that the fully in situ fabrication method gives a clean InAs/Nb interface. A clear Josephson supercurrent is observed in the current-voltage characteristics, which can be controlled by a bottom gate. The large excess current indicates a high junction transparency. Under microwave radiation, pronounced integer Shapiro steps are observed suggesting a sinusoidal current-phase relation. Owing to the large critical field of Nb, the Josephson supercurrent can be maintained to magnetic fields exceeding 1 T. Our results show that in situ prepared Nb/InAs nanowire contacts are very interesting candidates for superconducting quantum circuits requiring large magnetic fields.

Hole and Electron Effective Masses in Single InP Nanowires with a Wurtzite-Zincblende Homojunction.

The formation of wurtzite (WZ) phase in III-V nanowires (NWs) such as GaAs and InP is a complication hindering the growth of pure-phase NWs, but it can also be exploited to form NW homostructures consisting of alternate zincblende (ZB) and WZ segments. This leads to different forms of nanostructures, such as crystal-phase superlattices and quantum dots. Here, we investigate the electronic properties of the simplest, yet challenging, of such homostructures: InP NWs with a single homojunction between pure ZB and WZ segments. Polarization-resolved microphotoluminescence (µ-PL) measurements on single NWs provide a tool to gain insights into the interplay between NW geometry and crystal phase. We also exploit this homostructure to simultaneously measure effective masses of charge carriers and excitons in ZB and WZ InP NWs, reliably. Magneto-µ-PL measurements carried out on individual NWs up to 29 T at 77 K allow us to determine the free exciton reduced masses of the ZB and WZ crystal phases, showing the heavier character of the WZ phase, and to deduce the effective mass of electrons in ZB InP NWs (me= 0.080 m0). Finally, we obtain the reduced mass of light-hole excitons in WZ InP by probing the second optically permitted transition Γ7C ↔ Γ7uV with magneto-µ-PL measurements carried out at room temperature. This information is used to extract the experimental light-hole effective mass in WZ InP, which is found to be mlh = 0.26 m0, a value much smaller than the one of the heavy hole mass. Besides being a valuable test for band structure calculations, the knowledge of carrier masses in WZ and ZB InP is important in view of the optimization of the efficiency of solar cells, which is one of the main applications of InP NWs.

Preferred growth direction of III-V nanowires on differently oriented Si substrates.

One of the nanowire (NW) characteristics is its preferred elongation direction. Here, we investigated the impact of Si substrate crystal orientation on the growth direction of GaAs NWs. We first studied the self-catalyzed GaAs NW growth on Si (111) and Si (001) substrates. SEM observations show GaAs NWs on Si (001) are grown along four <111> directions without preference on one or some of them. This non-preferential NW growth on Si (001) is morphologically in contrast to the extensively reported vertical <111> preferred GaAs NW growth on Si (111) substrates. We propose a model based on the initial condition of an ideal Ga droplet formation on Si substrates and the surface free energy calculation which takes into account the dangling bond surface density for different facets. This model provides further understanding of the different preferences in the growth of GaAs NWs along selected <111> directions depending on the Si substrate orientation. To verify the prevalence of the model, NWs were grown on Si (311) substrates. The results are in good agreement with the three-dimensional mapping of surface free energy by our model. This general model can also be applied to predictions of NW preferred growth directions by the vapor-liquid-solid growth mode on other group IV and III-V substrates.

Checked patterned elemental distribution in AlGaAs nanowire branches via vapor-liquid-solid growth.

Morphology, crystal defects and crystal phase can significantly affect the elemental distribution of ternary nanowires (NWs). Here, we report the synergic impact of the structure and crystal phase on the composition of branched self-catalyzed AlxGa1-xAs NWs. Branching events were confirmed to increase with Al incorporation rising, while twinning and polytypism were observed to extend from the trunk to the branches, confirming the epitaxial nature of the latter. The growth mechanism of these structures has been ascribed to Ga accumulation at the concave sites on the rough shell. This is in agreement with the ab initio calculations which reveal Ga atoms tend to segregate at the trunk/branch interface. Notably, uncommon, intricate compositional variations are exposed in these branched NWs, where Ga-rich stripes parallel to the growth direction of the branches intersect with another set of periodic arrangements of Ga-rich stripes which are perpendicular to them, leading to the realization of an elemental checked pattern. The periodic variations perpendicular to the growth direction of the branches are caused by the constant rotation of the sample during growth whilst Ga-rich stripes along the growth direction of the branches are understood to be driven by the different nucleation energies and polarities on facets of different crystal phase at the interface between the catalyst droplets and the branched NW tip. These results lead to further comprehension of phase segregation and could assist in the compositional engineering in ternary NWs via harnessing this interesting phenomenon.

Heterostructure and Q-factor engineering for low-threshold and persistent nanowire lasing.

Continuous room temperature nanowire lasing from silicon-integrated optoelectronic elements requires careful optimisation of both the lasing cavity Q-factor and population inversion conditions. We apply time-gated optical interferometry to the lasing emission from high-quality GaAsP/GaAs quantum well nanowire laser structures, revealing high Q-factors of 1250 ± 90 corresponding to end-facet reflectivities of R = 0.73 ± 0.02. By using optimised direct-indirect band alignment in the active region, we demonstrate a well-refilling mechanism providing a quasi-four-level system leading to multi-nanosecond lasing and record low room temperature lasing thresholds (~6 µJ cm-2 pulse-1) for III-V nanowire lasers. Our findings demonstrate a highly promising new route towards continuously operating silicon-integrated nanolaser elements.

Defect Dynamics in Self-Catalyzed III-V Semiconductor Nanowires.

The droplet consumption step in self-catalyzed III-V semiconductor nanowires can produce material that contains a high density of line defects. Interestingly, these defects are often associated with twin boundaries and have null Burgers vector, i.e., no long-range strain field. Here, we analyze their stability by considering the forces that act on them and use in situ aberration corrected scanning transmission electron microscopy (STEM) to observe their behavior in GaAsP nanowires (NWs) using short annealing cycles. Their movement appears to be consistent with the thermally activated single- or double-kink mechanisms of dislocation glide, with velocities that do not exceed 1 nm s-1. We find that motion of individual defects depends on their size, position, and surrounding environment and set an upper limit to activation energy around 2 eV. The majority of defects (>70%) are removed by our postgrowth annealing for several seconds at temperatures in excess of 640 °C, suggesting that in situ annealing during growth at lower temperatures would significantly improve material quality. The remaining defects do not move at all and are thermodynamically stable in the nanowire.

Highly Strained III-V-V Coaxial Nanowire Quantum Wells with Strong Carrier Confinement.

Coaxial quantum wells (QWs) are ideal candidates for nanowire (NW) lasers, providing strong carrier confinement and allowing close matching of the cavity mode and gain medium. We report a detailed structural and optical study and the observation of lasing for a mixed group-V GaAsP NW with GaAs QWs. This system offers a number of potential advantages in comparison to previously studied common group-V structures ( e. g., AlGaAs/GaAs) including highly strained binary GaAs QWs, the absence of a lower band gap core region, and deep carrier potential wells. Despite the large lattice mismatch (∼1.7%), it is possible to grow defect-free GaAs coaxial QWs with high optical quality. The large band gap difference results in strong carrier confinement, and the ability to apply a high degree of compressive strain to the GaAs QWs is also expected to be beneficial for laser performance. For a non-fully optimized structure containing three QWs, we achieve low-temperature lasing with a low external (internal) threshold of 20 (0.9) µJ/cm2/pulse. In addition, a very narrow lasing line width of ∼0.15 nm is observed. These results extend the NW laser structure to coaxial III-V-V QWs, which are highly suitable as the platform for NW emitters.

Self-Formed Quantum Wires and Dots in GaAsP-GaAsP Core-Shell Nanowires.

Quantum structures designed using nanowires as a basis are excellent candidates to achieve novel design architectures. Here, triplets of quantum wires (QWRs) that form at the core-shell interface of GaAsP-GaAsP nanowires are reported. Their formation, on only three of the six vertices of the hexagonal nanowire, is governed by the three-fold symmetry of the cubic crystal on the (111) plane. In twinned nanowires, the QWRs are segmented, to alternating vertices, forming quantum dots (QDs). Simulations confirm the possibility of QWR and QD-like behavior from the respective regions. Optical measurements confirm the presence of two different types of quantum emitters in the twinned individual nanowires. The possibility to control the relative formation of QWRs or QDs, and resulting emission wavelengths of the QDs, by controlling the twinning of the nanowire core, opens up new possibilities for designing nanowire devices.

Engineering the Side Facets of Vertical [100] Oriented InP Nanowires for Novel Radial Heterostructures.

In addition to being grown on industry-standard orientation, vertical [100] oriented nanowires present novel families of facets and related cross-sectional shapes. These nanowires are engineered to achieve a number of facet combinations and cross-sectional shapes, by varying their growth parameters within ranges that facilitate vertical growth. In situ post-growth annealing technique is used to realise other combinations that are unattainable solely using growth parameters. Two examples of possible novel radial heterostructures grown on these vertical [100] oriented nanowire facets are presented, demonstrating their potential in future applications.

Growth and Fabrication of High-Quality Single Nanowire Devices with Radial p-i-n Junctions.

Nanowires (NWs) with radial p-i-n junction have advantages, such as large junction area and small influence from the surface states, which can lead to highly efficient material use and good device quantum efficiency. However, it is difficult to make high-quality core-shell NW devices, especially single NW devices. Here, the key factors during the growth and fabrication process that influence the quality of single core-shell p-i-n NW devices are studied using GaAs(P) NW photovoltaics as an example. By p-doping and annealing, good ohmic contact is achieved on NWs with a diameter as small as 50-60 nm. Single NW photovoltaics are subsequently developed and a record fill factor of 80.5% is shown. These results bring valuable information for making single NW devices, which can further benefit the development of high-density integration circuits.

Hybrid III-V/IV Nanowires: High-Quality Ge Shell Epitaxy on GaAs Cores.

The integration of optically active III-V and electronic-suitable IV materials on the same nanowire could provide a great potential for the combination of photonics and electronics in the nanoscale. In this Letter, we demonstrate the growth of GaAs/Ge core-shell nanowires on Si substrates by molecular beam epitaxy and investigate the radial and axial Ge epitaxy on GaAs nanowires in detail. High-quality core-shell nanowires with smooth side facets and dislocation-free, sharp interfaces are achieved. It is found that the low shell growth temperature leads to smoother side facets, while higher shell growth temperatures lead to more relaxed structures with significantly faceted sidewalls. The possibility of forming a III-V/IV heterostructure nanowire with a Ge section development in the axial direction of a GaAs nanowire using a Ga droplet is also revealed. These nanowires provide an ideal platform for nanoscale III-V/IV combination, which is promising for highly integrated photonic and electronic hybrid devices on a single chip.

Growth of Pure Zinc-Blende GaAs(P) Core-Shell Nanowires with Highly Regular Morphology.

The growth of self-catalyzed core-shell nanowires (NWs) is investigated systematically using GaAs(P) NWs. The defects in the core NW are found to be detrimental for the shell growth. These defects are effectively eliminated by introducing beryllium (Be) doping during the NW core growth and hence forming Be-Ga alloy droplets that can effectively suppress the WZ nucleation and facilitate the droplet consumption. Shells with pure zinc-blende crystal quality and highly regular morphology are successfully grown on the defect-free NW cores and demonstrated an enhancement of one order of magnitude for room-temperature emission compared to that of the defective shells. These results provide useful information on guiding the growth of high-quality shell, which can greatly enhance the NW device performance.

Bandgap Energy of Wurtzite InAs Nanowires.

InAs nanowires (NWs) have been grown on semi-insulating InAs (111)B substrates by metal-organic chemical vapor deposition catalyzed by 50, 100, and 150 nm-sized Au particles. The pure wurtzite (WZ) phase of these NWs has been attested by high-resolution transmission electron microscopy and selected area diffraction pattern measurements. Low temperature photoluminescence measurements have provided unambiguous and robust evidence of a well resolved, isolated peak at 0.477 eV, namely 59 meV higher than the band gap of ZB InAs. The WZ nature of this energy band has been demonstrated by high values of the polarization degree, measured in ensembles of NWs both as-grown and mechanically transferred onto Si and GaAs substrates, in agreement with the polarization selection rules for WZ crystals. The value of 0.477 eV found here for the bandgap energy of WZ InAs agrees well with theoretical calculations.

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.