Trapping Layers Prevent Dopant Segregation and Enable Remote Doping of Templated Self-Assembled InGaAs Nanowires.

Selective area epitaxy is a promising approach to define nanowire networks for topological quantum computing. However, it is challenging to concurrently engineer nanowire morphology, for carrier confinement, and precision doping, to tune carrier density. We report a strategy to promote Si dopant incorporation and suppress dopant diffusion in remote doped InGaAs nanowires templated by GaAs nanomembrane networks. Growth of a dilute AlGaAs layer following doping of the GaAs nanomembrane induces incorporation of Si that otherwise segregates to the growth surface, enabling precise control of the spacing between the Si donors and the undoped InGaAs channel; a simple model captures the influence of Al on the Si incorporation rate. Finite element modeling confirms that a high electron density is produced in the channel.

The implementation of thermal and UV nanoimprint lithography for selective area epitaxy.

Semiconductor nanowires (NWs) in horizontal configuration could provide a path for scalable NW-based devices. Bottom-up large-scale manufacturing of these nanostructures by selective area epitaxy (SAE) relies on precise nanopatterning of various shapes on the growth masks. Electron beam lithography offers an extraordinary accuracy suited for the purpose. However, this technique is not economically viable for large production as it has a low throughput and requires high investment and operational costs. Nanoimprint lithography (NIL) has the potential to reduce fabrication time and costs significantly while requiring less sophisticated equipment. In this work, we utilize both thermal and UV NIL for patterning substrates for SAE, elucidating the advantages and disadvantages of each lithography technique. We demonstrate the epitaxial growth of Ge and GaAs NWs on these substrates, where we observe high-quality mono-crystalline structures. Even though both processes can produce small uniform structures suitable for SAE, our results show that UV NIL proves to be superior and enables reliable and efficient patterning of sub-100 nm mask features at the wafer scale.

Coherent Hole Transport in Selective Area Grown Ge Nanowire Networks.

Holes in germanium nanowires have emerged as a realistic platform for quantum computing based on spin qubit logic. On top of the large spin-orbit coupling that allows fast qubit operation, nanowire geometry and orientation can be tuned to cancel out charge noise and hyperfine interaction. Here, we demonstrate a scalable approach to synthesize and organize Ge nanowires on silicon (100)-oriented substrates. Germanium nanowire networks are obtained by selectively growing on nanopatterned slits in a metalorganic vapor phase epitaxy system. Low-temperature electronic transport measurements are performed on nanowire Hall bar devices revealing high hole doping of ∼1018 cm-3 and mean free path of ∼10 nm. Quantum diffusive transport phenomena, universal conductance fluctuations, and weak antilocalization are revealed through magneto transport measurements yielding a coherence and a spin-orbit length of the order of 100 and 10 nm, respectively.

Stoichiometry modulates the optoelectronic functionality of zinc phosphide (Zn3-xP2+x).

Predictive synthesis-structure-property relationships are at the core of materials design for novel applications. In this regard, correlations between the compositional stoichiometry variations and functional properties are essential for enhancing the performance of devices based on these materials. In this work, we investigate the effect of stoichiometry variations and defects on the structural and optoelectronic properties of monocrystalline zinc phosphide (Zn3P2), a promising compound for photovoltaic applications. We use experimental methods, such as electron and X-ray diffraction and Raman spectroscopy, along with density functional theory calculations, to showcase the favorable creation of P interstitial defects over Zn vacancies in P-rich and Zn-poor compositional regions. Photoluminescence and absorption measurements show that these defects create additional energy levels at about 180 meV above the valence band. Furthermore, they lead to the narrowing of the bandgap, due to the creation of band tails in the region of around 10-20 meV above the valence and below the conduction band. The ability of zinc phosphide to form off-stoichiometric compounds provides a new promising opportunity for tunable functionality that benefits applications. In that regard, this study is crucial for the further development of zinc phosphide and its application in optoelectronic and photovoltaic devices, and should pave the way for defect engineering in this kind of material.

Selective area epitaxy of GaAs: the unintuitive role of feature size and pitch.

Selective area epitaxy (SAE) provides the path for scalable fabrication of semiconductor nanostructures in a device-compatible configuration. In the current paradigm, SAE is understood as localized epitaxy, and is modelled by combining planar and self-assembled nanowire growth mechanisms. Here we use GaAs SAE as a model system to provide a different perspective. First, we provide evidence of the significant impact of the annealing stage in the calculation of the growth rates. Then, by elucidating the effect of geometrical constraints on the growth of the semiconductor crystal, we demonstrate the role of adatom desorption and resorption beyond the direct-impingement and diffusion-limited regime. Our theoretical model explains the effect of these constraints on the growth, and in particular why the SAE growth rate is highly sensitive to the pattern geometry. Finally, the disagreement of the model at the largest pitch points to non-negligible multiple adatom recycling between patterned features. Overall, our findings point out the importance of considering adatom diffusion, adsorption and desorption dynamics in designing the SAE pattern to create pre-determined nanoscale structures across a wafer. These results are fundamental for the SAE process to become viable in the semiconductor industry.

Simultaneous Selective Area Growth of Wurtzite and Zincblende Self-Catalyzed GaAs Nanowires on Silicon.

Selective area epitaxy constitutes a mainstream method to obtain reproducible nanomaterials. As a counterpart, self-assembly allows their growth without costly substrate preparation, with the drawback of uncontrolled positioning. We propose a mixed approach in which self-assembly is limited to reduced regions on a patterned silicon substrate. While nanowires grow with a wide distribution of diameters, we note a mostly binary occurrence of crystal phases. Self-catalyzed GaAs nanowires form in either a wurtzite or zincblende phase in the same growth run. Quite surprisingly, thicker nanowires are wurtzite and thinner nanowires are zincblende, while the common view predicts the reverse trend. We relate this phenomenon to the influx of Ga adatoms by surface diffusion, which results in different contact angles of Ga droplets. We demonstrate the wurtzite phase of thick GaAs NWs up to 200 nm in diameter in the Au-free approach, which has not been achieved so far to our knowledge.

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.

Raman spectroscopy and lattice dynamics calculations of tetragonally-structured single crystal zinc phosphide (Zn3P2) nanowires.

Earth-abundant and low-cost semiconductors, such as zinc phosphide (Zn3P2), are promising candidates for the next generation photovoltaic applications. However, synthesis on commercially available substrates, which favors the formation of defects, and controllable doping are challenging drawbacks that restrain device performance. Better assessment of relevant properties such as structure, crystal quality and defects will allow faster advancement of Zn3P2, and in this sense, Raman spectroscopy can play an invaluable role. In order to provide a complete Raman spectrum reference of Zn3P2, this work presents a comprehensive analysis of vibrational properties of tetragonally-structured Zn3P2 (space group P42/nmc) nanowires, from both experimental and theoretical perspectives. Low-temperature, high-resolution Raman polarization measurements have been performed on single-crystalline nanowires. Different polarization configurations have allowed selective enhancement of A1g, B1g and Eg Raman modes, while B2g modes were identified from complementary unpolarized Raman measurements. Simultaneous deconvolution of all Raman spectra with Lorentzian curves has allowed identification of 33 peaks which have been assigned to 34 (8 A1g + 9 B1g + 3 B2g + 14 Eg) out of the 39 theoretically predicted eigenmodes. The experimental results are in good agreement with the vibrational frequencies that have been computed by first-principles calculations based on density functional theory. Three separate regions were observed in the phonon dispersion diagram: (i) low-frequency region (<210 cm-1) which is dominated by Zn-related vibrations, (ii) intermediate region (210-225 cm-1) which represents a true phonon gap with no observed vibrations, and (iii) high-frequency region (>225 cm-1) which is attributed to primarily P-related vibrations. The analysis of vibrational patterns has shown that non-degenerate modes involve mostly atomic motion along the long crystal axis (c-axis), while degenerate modes correspond primarily to in-plane vibrations, perpendicular to the long c-axis. These results provide a detailed reference for identification of the tetragonal Zn3P2 phase and can be used for building Raman based methodologies for effective defect screening of bulk materials and films, which might contain structural inhomogeneities.

Raman tensor of zinc-phosphide (Zn3P2): from polarization measurements to simulation of Raman spectra.

Zinc phosphide (Zn3P2) is a II-V compound semiconductor with promising photovoltaic and thermoelectric applications. Its complex structure is susceptible to facile defect formation, which plays a key role in further optimization of the material. Raman spectroscopy can be effectively used for defect characterization. However, the Raman tensor of Zn3P2, which determines the intensity of Raman peaks and anisotropy of inelastic light scattering, is still unknown. In this paper, we use angle-resolved polarization Raman measurements on stoichiometric monocrystalline Zn3P2 thin films to obtain the Raman tensor of Zn3P2. This has allowed determination of the Raman tensor elements characteristic for the A1g, B1g and B2g vibrational modes. These results have been compared with the theoretically obtained Raman tensor elements and simulated Raman spectra from the lattice-dynamics calculations using first-principles force constants. Excellent agreement is found between the experimental and simulated Raman spectra of Zn3P2 for various polarization configurations, providing a platform for future characterization of the defects in this material.

Quantitative Nanoscale Absorption Mapping: A Novel Technique To Probe Optical Absorption of Two-Dimensional Materials.

Two-dimensional semiconductors, in particular transition metal dichalcogenides and related heterostructures, have gained increasing interest as they constitute potential new building blocks for the next generation of electronic and optoelectronic applications. In this work, we develop a novel nondestructive and noncontact technique for mapping the absorption properties of 2D materials, by taking advantage of the underlying substrate cathodoluminescence emission. We map the quantitative absorption of MoS2 and MoSe2 monolayers, obtained on sapphire and oxidized silicon, with nanoscale resolution. We extend our technique to the characterization of the absorption properties of MoS2/MoSe2 van der Waals heterostructures. We demonstrate that interlayer excitonic phenomena enhance the absorption in the UV range. Our technique also highlights the presence of defects such as grain boundaries and ad-layers. We provide measurements on the absorption of grain boundaries in monolayer MoS2 at different merging angles. We observe a higher absorption yield of randomly oriented monolayers with respect to 60° rotated monolayers. This work opens up a new possibility for characterizing the functional properties two-dimensional semiconductors at the nanoscale.

Remote Doping of Scalable Nanowire Branches.

Selective-area epitaxy provides a path toward high crystal quality, scalable, complex nanowire networks. These high-quality networks could be used in topological quantum computing as well as in ultrafast photodetection schemes. Control of the carrier density and mean free path in these devices is key for all of these applications. Factors that affect the mean free path include scattering by surfaces, donors, defects, and impurities. Here, we demonstrate how to reduce donor scattering in InGaAs nanowire networks by adopting a remote-doping strategy. Low-temperature magnetotransport measurements indicate weak anti-localization-a signature of strong spin-orbit interaction-across a nanowire Y-junction. This work serves as a blueprint for achieving remotely doped, ultraclean, and scalable nanowire networks for quantum technologies.

In-situ reflectometry to monitor locally-catalyzed initiation and growth of nanowire assemblies.

We investigate in-situ laser reflectometry for measuring the axial growth rate in chemical vapor deposition of assemblies of well-aligned vertical germanium nanowires grown epitaxially on single crystal substrates. Finite difference frequency domain optical simulations were performed in order to facilitate quantitative analysis and interpretation of the measured reflectivity data. The results show an insensitivity of the reflected intensity oscillation period to nanowire diameter and density within the range of experimental conditions investigated. Compared to previous quantitative in-situ measurements performed on III-V nanowire arrays, which showed two distinct rate regimes, we observe a constant, steady-state nanowire growth rate. Furthermore, we show that the measured reflectivity decay can be used to determine the germanium nanowire nucleation time with good precision. This technique provides an avenue to monitor growth of nanowires in a variety of materials systems and growth conditions.

Time-resolved open-circuit conductive atomic force microscopy for direct electromechanical characterisation.

Studying nanomaterial piezoelectricity and triboelectricity is attractive for energy and sensing applications. However, quantitative characterisation of electromechanical effects in nanomaterials is challenging due to practical limitations and possible combination of effects, resulting in contradicting reports at times. When it comes to piezoelectricity at the nanoscale, piezoresponse force microscopy (PFM) is the default characterisation tool. In PFM the converse piezoelectric effect is measured - the conversion from electrical signal to mechanical response. However, there is an underlying desire to measure the direct piezoelectric effect - conversion of mechanical deformation to an electrical signal. This corresponds to energy harvesting and sensing. Here we present time-resolved open-circuit conductive atomic force microscopy (cAFM) as a new methodology to carry out direct electromechanical characterisation. We show, both theoretically and experimentally, that the standard short-circuit cAFM mode is inadequate for piezoelectric characterisation, and that resulting measurements are governed by competing mechanisms. We apply the new methodology to nanowires of GaAs, an important semiconductor, with relatively low piezoelectric coefficients. The results suggest that time-resolved operation distinguishes between triboelectric and piezoelectric signals, and that by measuring the open-circuit voltage rather than short-circuit current, the new methodology allows quantitative characterisation of the vertical piezoelectric coefficient. The result for GaAs nanowires, ∼ 1-3 pm V-1, is in good agreement with existing knowledge and theory. This method represents a significant advance in understanding the coexistence of different electromechanical effects, and in quantitative piezoelectric nanoscale characterisation. The easy implementation will enable better understanding of electromechanics at the nanoscale.

Single-Crystalline γ-Ga2S3 Nanotubes via Epitaxial Conversion of GaAs Nanowires.

The chemical transformation of nanowire templates into nanotubes is a promising avenue toward hollow one-dimensional (1D) nanostructures. To date, high-quality single crystalline tubes of nonlayered inorganic crystals have been obtained by solid-state reactions in diffusion couples of nanowires with deposited thin film shells, but this approach presents issues in achieving single-phase tubes with a desired stoichiometry. Chemical transformations with reactants supplied from the gas- or vapor-phase can avoid these complications, allowing single-phase nanotubes to be obtained through self-termination of the reaction once the sacrificial template has been consumed. Here, we demonstrate the realization of this scenario with the transformation of zincblende GaAs nanowires into single-crystalline cubic γ-Ga2S3 nanotubes by reaction with sulfur vapor. The conversion proceeds via the formation of epitaxial GaAs-Ga2S3 core-shell structures, vacancy injection and aggregation into Kirkendall voids, elastic relaxation of the detached Ga2S3 shell, and finally complete incorporation of Ga in a crystalline chalcogenide tube. Absorption and luminescence spectroscopy on individual nanotubes show optoelectronic properties, notably a ∼3.1 eV bandgap and intense band-edge and near band-edge emission consistent with high-quality single crystals, along with transitions between gap-states due to the inherent cation-vacancy defect structure of Ga2S3. Our work establishes the transformation of nanowires via vapor-phase reactions as a viable approach for forming single-crystalline hollow 1D nanostructures with promising properties.

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.

Extraction of p-n junction properties and series resistance in GaAs nanowire-based solar cells using light concentration.

Series resistance in solar cells limit their maximum conversion efficiency and thus should be minimized. Generally, such losses originate from deficiencies at the contact or absorber level. Quantifying them is the first step for tackling its reduction. In this work, we provide a new way to assess the series resistance in nanowire-based solar cells, which significantly underperforms predicted theoretical efficiency. We illuminate the devices at different levels of light intensity (from 1 to 1000 suns), which gives us insight in the carrier transport and series losses mechanism. We demonstrate the method on a device obtained by self-assembled GaAs nanowire p-n junction arrays on silicon. This analysis method provides a platform to distinguish the intrinsic response of the nanowire p-n junction from the series resistance effects. More generally, we provide a means of optimizing the efficiency in next generation solar cells, where contacts still have to be developed.

Increasing N content in GaNAsP nanowires suppresses the impact of polytypism on luminescence.

Cathodoluminescence (CL) and micro-photoluminescence spectroscopies are employed to investigate effects of structural defects on carrier recombination in GaNAsP nanowires (NWs) grown by molecular beam epitaxy on Si substrates. In the NWs with a low N content of 0.08%, these defects are found to promote non-radiative (NR) recombination, which causes spatial variation of the CL peak position and its intensity. Unexpectedly, these detrimental effects can be suppressed even by a small increase in the nitrogen composition from 0.08% to 0.12%. This is attributed to more efficient trapping of excited carriers/excitons to the localized states promoted by N-induced localization and also the presence of other NR channels. At room temperature, the structural defects no longer dominate in carrier recombination even in the NWs with the lower nitrogen content, likely due to increasing importance of other recombination channels. Our work underlines the need in eliminating important thermally activated NR defects, other than the structural defects, for future optoelectronic applications of these NWs.

High Electron Mobility and Insights into Temperature-Dependent Scattering Mechanisms in InAsSb Nanowires.

InAsSb nanowires are promising elements for thermoelectric devices, infrared photodetectors, high-speed transistors, as well as thermophotovoltaic cells. By changing the Sb alloy fraction the mid-infrared bandgap energy and thermal conductivity may be tuned for specific device applications. Using both terahertz and Raman noncontact probes, we show that Sb alloying increases the electron mobility in the nanowires by over a factor of 3 from InAs to InAs0.65Sb0.35. We also extract the temperature-dependent electron mobility via both terahertz and Raman spectroscopy, and we report the highest electron mobilities for InAs0.65Sb0.35 nanowires to date, exceeding 16,000 cm2 V-1 s-1 at 10 K.

Bistability of Contact Angle and Its Role in Achieving Quantum-Thin Self-Assisted GaAs nanowires.

Achieving quantum confinement by bottom-up growth of nanowires has so far been limited to the ability of obtaining stable metal droplets of radii around 10 nm or less. This is within reach for gold-assisted growth. Because of the necessity to maintain the group III droplets during growth, direct synthesis of quantum sized structures becomes much more challenging for self-assisted III-V nanowires. In this work, we elucidate and solve the challenges that involve the synthesis of gallium-assisted quantum-sized GaAs nanowires. We demonstrate the existence of two stable contact angles for the gallium droplet on top of GaAs nanowires. Contact angle around 130° fosters a continuous increase in the nanowire radius, while 90° allows for the stable growth of ultrathin tops. The experimental results are fully consistent with our model that explains the observed morphological evolution under the two different scenarios. We provide a generalized theory of self-assisted III-V nanowires that describes simultaneously the droplet shape relaxation and the NW radius evolution. Bistability of the contact angle described here should be the general phenomenon that pertains for any vapor-liquid-solid nanowires and significantly refines our picture of how nanowires grow. Overall, our results suggest a new path for obtaining ultrathin one-dimensional III-V nanostructures for studying lateral confinement of carriers.