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.

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.

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.

Questioning liquid droplet stability on nanowire tips: from theory to experiment.

Liquid droplets sitting on nanowire (NW) tips constitute the starting point of the vapor-liquid-solid method of NW growth. Shape and volume of the droplet have been linked to a variety of growth phenomena ranging from the modification of growth direction, NW orientation, crystal phase, and even polarity. In this work we focus on numerical and theoretical analysis of the stability of liquid droplets on NW tips, explaining the peculiarity of this condition with respect to the wetting of planar surfaces. We highlight the role of droplet pinning at the tip in engineering the contact angle. Experimental results on the characteristics of In droplets of variable volume sitting on the tips or side facets of InAs NWs are also provided. This work contributes to the fundamental understanding of the nature of droplets contact angle at the tip of NWs and to the improvement of the engineering of such nanostructures.

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.

Anisotropic-Strain-Induced Band Gap Engineering in Nanowire-Based Quantum Dots.

Tuning light emission in bulk and quantum structures by strain constitutes a complementary method to engineer functional properties of semiconductors. Here, we demonstrate the tuning of light emission of GaAs nanowires and their quantum dots up to 115 meV by applying strain through an oxide envelope. We prove that the strain is highly anisotropic and clearly results in a component along the NW longitudinal axis, showing good agreement with the equations of uniaxial stress. We further demonstrate that the strain strongly depends on the oxide thickness, the oxide intrinsic strain, and the oxide microstructure. We also show that ensemble measurements are fully consistent with characterizations at the single-NW level, further elucidating the general character of the findings. This work provides the basic elements for strain-induced band gap engineering and opens new avenues in applications where a band-edge shift is necessary.

Template-Assisted Scalable Nanowire Networks.

Topological qubits based on Majorana Fermions have the potential to revolutionize the emerging field of quantum computing by making information processing significantly more robust to decoherence. Nanowires are a promising medium for hosting these kinds of qubits, though branched nanowires are needed to perform qubit manipulations. Here we report a gold-free templated growth of III-V nanowires by molecular beam epitaxy using an approach that enables patternable and highly regular branched nanowire arrays on a far greater scale than what has been reported thus far. Our approach relies on the lattice-mismatched growth of InAs on top of defect-free GaAs nanomembranes yielding laterally oriented, low-defect InAs and InGaAs nanowires whose shapes are determined by surface and strain energy minimization. By controlling nanomembrane width and growth time, we demonstrate the formation of compositionally graded nanowires with cross-sections less than 50 nm. Scaling the nanowires below 20 nm leads to the formation of homogeneous InGaAs nanowires, which exhibit phase-coherent, quasi-1D quantum transport as shown by magnetoconductance measurements. These results are an important advance toward scalable topological quantum computing.

Nanoscale Mapping of Light Emission in Nanospade-Based InGaAs Quantum Wells Integrated on Si(100): Implications for Dual Light-Emitting Devices.

III-V semiconductors outperform Si in many optoelectronics applications due to their high carrier mobility, efficient light emission and absorption processes, and the possibility to engineer their band gap through alloying. However, complementing Si technology with III-V semiconductors by integration on Si(100) remains a challenge still today. Vertical nanospades (NSPDs) are quasi-bi-crystal III-V nanostructures that grow on Si(100). Here, we showcase the potential of these structures in optoelectronics application by demonstrating InGaAs heterostructures on GaAs NSPDs that exhibit bright emission in the near-infrared region. Using cathodoluminescence hyperspectral imaging, we are able to study light emission properties at a few nanometers of spatial resolution, well below the optical diffraction limit. We observe a symmetric spatial luminescence splitting throughout the NSPD. We correlate this characteristic to the structure's crystal nature, thus opening new perspectives for dual wavelength light-emitting diode structures. This work paves the path for integrating optically active III-V structures on the Si(100) platform.

GaAs nanowires on Si nanopillars: towards large scale, phase-engineered arrays.

Large-scale patterning for vapor-liquid-solid growth of III-V nanowires is a challenge given the required feature size for patterning (45 to 60 nm holes). In fact, arrays are traditionally manufactured using electron-beam lithography,for which processing times increase greatly when expanding the exposure area. In order to bring nanowire arrays one step closer to the wafer-scale we take a different approach and replace patterned nanoscale holes with Si nanopillar arrays. The method is compatible with photolithography methods such as phase-shift lithography or deep ultraviolet (DUV) stepper lithography. We provide clear evidence on the advantage of using nanopillars as opposed to nanoscale holes both for the control on the growth mechanisms and for the scalability. We identify the engineering of the contact angle as the key parameter to optimize the yield. In particular, we demonstrate how nanopillar oxidation is key to stabilize the Ga catalyst droplet and engineer the contact angle. We demonstrate how the position of the triple phase line at the SiO2/Si as opposed to the SiO2/vacuum interface is central for a successful growth. We compare our experiments with simulations performed in surface evolver™ and observe a strong correlation. Large-scale arrays using phase-shift lithography result in a maximum local vertical yield of 67% and a global chip-scale yield of 40%. We believe that, through a greater control over key processing steps typically achieved in a semiconductor fab it is possible to push this yield to 90+% and open perspectives for deterministic nanowire phase engineering at the wafer-scale.

III-V Integration on Si(100): Vertical Nanospades.

III-V integration on Si(100) is a challenge: controlled vertical vapor liquid solid nanowire growth on this platform has not been reported so far. Here we demonstrate an atypical GaAs vertical nanostructure on Si(100), coined nanospade, obtained by a nonconventional droplet catalyst pinning. The Ga droplet is positioned at the tip of an ultrathin Si pillar with a radial oxide envelope. The pinning at the Si/oxide interface allows the engineering of the contact angle beyond the Young-Dupré equation and the growth of vertical nanospades. Nanospades exhibit a virtually defect-free bicrystalline nature. Our growth model explains how a pentagonal twinning event at the initial stages of growth provokes the formation of the nanospade. The optical properties of the nanospades are consistent with the high crystal purity, making these structures viable for use in integration of optoelectronics on the Si(100) platform.

Optimizing the yield of A-polar GaAs nanowires to achieve defect-free zinc blende structure and enhanced optical functionality.

Compound semiconductors exhibit an intrinsic polarity, as a consequence of the ionicity of their bonds. Nanowires grow mostly along the (111) direction for energetic reasons. Arsenide and phosphide nanowires grow along (111)B, implying a group V termination of the (111) bilayers. Polarity engineering provides an additional pathway to modulate the structural and optical properties of semiconductor nanowires. In this work, we demonstrate for the first time the growth of Ga-assisted GaAs nanowires with (111)A-polarity, with a yield of up to ∼50%. This goal is achieved by employing highly Ga-rich conditions which enable proper engineering of the energies of A and B-polar surfaces. We also show that A-polarity growth suppresses the stacking disorder along the growth axis. This results in improved optical properties, including the formation of AlGaAs quantum dots with two orders or magnitude higher brightness. Overall, this work provides new grounds for the engineering of nanowire growth directions, crystal quality and optical functionality.