An Ultrafast Switchable Terahertz Polarization Modulator Based on III-V Semiconductor Nanowires.

Progress in the terahertz (THz) region of the electromagnetic spectrum is undergoing major advances, with advanced THz sources and detectors being developed at a rapid pace. Yet, ultrafast THz communication is still to be realized, owing to the lack of practical and effective THz modulators. Here, we present a novel ultrafast active THz polarization modulator based on GaAs semiconductor nanowires arranged in a wire-grid configuration. We utilize an optical pump-terahertz probe spectroscopy system and vary the polarization of the optical pump beam to demonstrate ultrafast THz modulation with a switching time of less than 5 ps and a modulation depth of -8 dB. We achieve an extinction of over 13% and a dynamic range of -9 dB, comparable to microsecond-switchable graphene- and metamaterial-based THz modulators, and surpassing the performance of optically switchable carbon nanotube THz polarizers. We show a broad bandwidth for THz modulation between 0.1 and 4 THz. Thus, this work presents the first THz modulator which combines not only a large modulation depth but also a broad bandwidth and picosecond time resolution for THz intensity and phase modulation, making it an ideal candidate for ultrafast THz communication.

Growth of Catalyst-Free Epitaxial InAs Nanowires on Si Wafers Using Metallic Masks.

Development of heteroepitaxy growth of catalyst-free vertical III-V nanowires on Si wafers is highly desirable for future nanoscale Si-based electronic and optoelectronic devices. In this study, a proof-of-concept approach is developed for catalyst-free heteroepitaxy growth of InAs nanowires on Si wafers. Before the growth of InAs nanowires, a Si-compatible metallic film with a thickness of several tens of nanometers was predeposited on a Si wafer and then annealed to form nanosize openings so as to obtain a metallic mask. These nano-openings exposed the surface of the Si wafer, which allowed subsequent nucleation and growth of epitaxial InAs nanowires directly on the surface of the Si wafer. The small size of the nano-openings limits the lateral growth of the nanostructures but promotes their axial growth. Through this approach, catalyst-free InAs nanowires were grown on both Si (111) and (001) wafers successfully at different growth temperatures. In particular, ultralong defect-free InAs nanowires with the wurtzite structure were grown the Si (111) wafers at 550 °C using the Ni mask. This study offers a simple, cost-effective, and scalable method to grow catalyst-free III-V nanowires on Si wafers. The simplicity of the approach opens a new avenue for the growth and integration of catalyst-free high-quality heteroepitaxial III-V nanowires on Si wafers.

Thermal Delocalization of Excitons in GaAs/AlGaAs Quantum Well Tube Nanowires.

We use temperature-dependent photoluminescence (PL), photoluminescence imaging, and time-resolved photoluminescence measurements to gain insights into the localization of excitons in single 2 nm GaAs/AlGaAs quantum well tube nanowires. PL spectra reveal the coexistence of localized and delocalized states at low temperatures, with narrow quantum dot-like emission lines on the high energy side of a broad emission band, and delocalized states on the low energy side. We find that the high energy QD-like emissions are metastable, disappearing at higher temperatures with only delocalized states (quantum well tube ground states) surviving. By comparing temperature- and time-dependent PL, we develop a theoretical model which provides insights into the confinement potentials and relaxation dynamics which localize the excitons in these quantum well tube nanowires.

Effect of a High Density of Stacking Faults on the Young's Modulus of GaAs Nanowires.

Stacking faults (SFs) are commonly observed crystalline defects in III-V semiconductor nanowires (NWs) that affect a variety of physical properties. Understanding the effect of SFs on NW mechanical properties is critical to NW applications in nanodevices. In this study, the Young's moduli of GaAs NWs with two distinct structures, defect-free single crystalline wurtzite (WZ) and highly defective wurtzite containing a high density of SFs (WZ-SF), are investigated using combined in situ compression transmission electron microscopy and finite element analysis. The Young's moduli of both WZ and WZ-SF GaAs NWs were found to increase with decreasing diameter due to the increasing volume fraction of the native oxide shell. The presence of a high density of SFs was further found to increase the Young's modulus by 13%. This stiffening effect of SFs is attributed to the change in the interatomic bonding configuration at the SFs.

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.

Quantum Confined Stark Effect in a GaAs/AlGaAs Nanowire Quantum Well Tube Device: Probing Exciton Localization.

In this Letter, we explore the nature of exciton localization in single GaAs/AlGaAs nanowire quantum well tube (QWT) devices using photocurrent (PC) spectroscopy combined with simultaneous photoluminescence (PL) and photoluminescence excitation (PLE) measurements. Excitons confined to GaAs quantum well tubes of 8 and 4 nm widths embedded into an AlGaAs barrier are seen to ionize at high bias levels. Spectroscopic signatures of the ground and excited states confined to the QWT seen in PL, PLE, and PC data are consistent with simple numerical calculations. The demonstration of good electrical contact with the QWTs enables the study of Stark effect shifts in the sharp emission lines of excitons localized to quantum dot-like states within the QWT. Atomic resolution cross-sectional TEM measurements and an analysis of the quantum confined Stark effect of these dots provide insights into the nature of the exciton localization in these nanostructures.

Determination of Young's Modulus of Ultrathin Nanomaterials.

Determination of the elastic modulus of nanostructures with sizes at several nm range is a challenge. In this study, we designed an experiment to measure the elastic modulus of amorphous Al2O3 films with thicknesses varying between 2 and 25 nm. The amorphous Al2O3 was in the form of a shell, wrapped around GaAs nanowires, thereby forming an effective core/shell structure. The GaAs core comprised a single crystal structure with a diameter of 100 nm. Combined in situ compression transmission electron microscopy and finite element analysis were used to evaluate the elastic modulus of the overall core/shell nanowires. A core/shell model was applied to deconvolute the elastic modulus of the Al2O3 shell from the core. The results indicate that the elastic modulus of amorphous Al2O3 increases significantly when the thickness of the layer is smaller than 5 nm. This novel nanoscale material can be attributed to the reconstruction of the bonding at the surface of the material, coupled with the increase of the surface-to-volume ratio with nanoscale dimensions. Moreover, the experimental technique and analysis methods presented in this study may be extended to measure the elastic modulus of other materials with dimensions of just several nanometers.

Emergence of localized states in narrow GaAs/AlGaAs nanowire quantum well tubes.

We use low-temperature photoluminescence, photoluminescence excitation, and photoluminescence imaging spectroscopy to explore the optical and electronic properties of GaAs/AlGaAs quantum well tube (QWT) heterostructured nanowires (NWs). We find that GaAs QWTs with widths >5 nm have electronic states which are delocalized and continuous along the length of the NW. As the NW QWT width decreases from 5 to 1.5 nm, only a single electron state is bound to the well, and no optical excitations to a confined excited state are present. Simultaneously, narrow emission lines (fwhm < 600 µeV) appear which are localized to single spatial points along the length of the NW. We find that these quantum-dot-like states broaden at higher temperatures and quench at temperatures above 80 K. The lifetimes of these localized states are observed to vary from dot to dot from 160 to 400 ps. The presence of delocalized states and then localized states as the QWTs become more confined suggests both opportunities and challenges for possible incorporation into quantum-confined device structures.

Electron mobilities approaching bulk limits in "surface-free" GaAs nanowires.

Achieving bulk-like charge carrier mobilities in semiconductor nanowires is a major challenge facing the development of nanowire-based electronic devices. Here we demonstrate that engineering the GaAs nanowire surface by overcoating with optimized AlGaAs shells is an effective means of obtaining exceptionally high carrier mobilities and lifetimes. We performed measurements of GaAs/AlGaAs core-shell nanowires using optical pump-terahertz probe spectroscopy: a noncontact and accurate probe of carrier transport on ultrafast time scales. The carrier lifetimes and mobilities both improved significantly with increasing AlGaAs shell thickness. Remarkably, optimized GaAs/AlGaAs core-shell nanowires exhibited electron mobilities up to 3000 cm(2) V(-1) s(-1), reaching over 65% of the electron mobility typical of high quality undoped bulk GaAs at equivalent photoexcited carrier densities. This points to the high interface quality and the very low levels of ionized impurities and lattice defects in these nanowires. The improvements in mobility were concomitant with drastic improvements in photoconductivity lifetime, reaching 1.6 ns. Comparison of photoconductivity and photoluminescence dynamics indicates that midgap GaAs surface states, and consequently surface band-bending and depletion, are effectively eliminated in these high quality heterostructures.

Polarity-driven nonuniform composition in InGaAs nanowires.

Manipulating the composition and morphology of semiconductor nanowires in a precisely controlled fashion is critical in developing nanowire devices. This is particularly true for ternary III-V nanowires. Many studies have shown the complexities within those nanowires. Here we report our findings of compositional irregularity in the shells of core-shell InGaAs nanowires with zinc-blende structure. Such an effect is caused by the crystal polarity within III-V zinc-blende lattice and the one-dimensional nature of nanowires that allows the formation of opposite polar surfaces simultaneously on the nanowire sidewalls. This polarity-driven effect in III-V nanowires may be utilized in manipulating the composition and morphology of III-V nanowires for device applications.

Direct observation of charge-carrier heating at WZ-ZB InP nanowire heterojunctions.

We have investigated the dynamics of hot charge carriers in InP nanowire ensembles containing a range of densities of zinc-blende inclusions along the otherwise wurtzite nanowires. From time-dependent photoluminescence spectra, we extract the temperature of the charge carriers as a function of time after nonresonant excitation. We find that charge-carrier temperature initially decreases rapidly with time in accordance with efficient heat transfer to lattice vibrations. However, cooling rates are subsequently slowed and are significantly lower for nanowires containing a higher density of stacking faults. We conclude that the transfer of charges across the type II interface is followed by release of additional energy to the lattice, which raises the phonon bath temperature above equilibrium and impedes the carrier cooling occurring through interaction with such phonons. These results demonstrate that type II heterointerfaces in semiconductor nanowires can sustain a hot charge-carrier distribution over an extended time period. In photovoltaic applications, such heterointerfaces may hence both reduce recombination rates and limit energy losses by allowing hot-carrier harvesting.

Electronic properties of GaAs, InAs and InP nanowires studied by terahertz spectroscopy.

We have performed a comparative study of ultrafast charge carrier dynamics in a range of III-V nanowires using optical pump-terahertz probe spectroscopy. This versatile technique allows measurement of important parameters for device applications, including carrier lifetimes, surface recombination velocities, carrier mobilities and donor doping levels. GaAs, InAs and InP nanowires of varying diameters were measured. For all samples, the electronic response was dominated by a pronounced surface plasmon mode. Of the three nanowire materials, InAs nanowires exhibited the highest electron mobilities of 6000 cm² V⁻¹ s⁻¹, which highlights their potential for high mobility applications, such as field effect transistors. InP nanowires exhibited the longest carrier lifetimes and the lowest surface recombination velocity of 170 cm s⁻¹. This very low surface recombination velocity makes InP nanowires suitable for applications where carrier lifetime is crucial, such as in photovoltaics. In contrast, the carrier lifetimes in GaAs nanowires were extremely short, of the order of picoseconds, due to the high surface recombination velocity, which was measured as 5.4 × 105 cm s⁻¹. These findings will assist in the choice of nanowires for different applications, and identify the challenges in producing nanowires suitable for future electronic and optoelectronic devices.

Strong carrier lifetime enhancement in GaAs nanowires coated with semiconducting polymer.

The ultrafast charge carrier dynamics in GaAs/conjugated polymer type II heterojunctions are investigated using time-resolved photoluminescence spectroscopy at 10 K. By probing the photoluminescence at the band edge of GaAs, we observe strong carrier lifetime enhancement for nanowires blended with semiconducting polymers. The enhancement is found to depend crucially on the ionization potential of the polymers with respect to the Fermi energy level at the surface of the GaAs nanowires. We attribute these effects to electron doping by the polymer which reduces the unsaturated surface-state density in GaAs. We find that when the surface of nanowires is terminated by native oxide, the electron injection across the interface is greatly reduced and such surface doping is absent. Our results suggest that surface engineering via π-conjugated polymers can substantially improve the carrier lifetime in nanowire hybrid heterojunctions with applications in photovoltaics and nanoscale photodetectors.

Defect-free <110> zinc-blende structured InAs nanowires catalyzed by palladium.

We report the epitaxial growth of defect-free zinc-blende structured InAs nanowires on GaAs{111}(B) substrates using palladium catalysts in a metal-organic chemical vapor deposition reactor. Through detailed morphological, structural, and chemical characterizations using electron microscopy, it is found that these defect-free InAs nanowires grew along the <1[combining overline]1[combining overline]0> directions with four low-energy {111} faceted side walls and {1[combining overline]1[combining overline]3[combining overline]} nanowire/catalyst interfaces. It is anticipated that these defect-free <1[combining overline]1[combining overline]0> nanowires benefit from the fact that the nanowire/catalyst interfaces does not contain the {111} planes, and the nanowire growth direction is not along the <111> directions. This study provides an effective approach to control the crystal structure and quality of epitaxial III-V nanowires.

Ultralow surface recombination velocity in InP nanowires probed by terahertz spectroscopy.

Using transient terahertz photoconductivity measurements, we have made noncontact, room temperature measurements of the ultrafast charge carrier dynamics in InP nanowires. InP nanowires exhibited a very long photoconductivity lifetime of over 1 ns, and carrier lifetimes were remarkably insensitive to surface states despite the large nanowire surface area-to-volume ratio. An exceptionally low surface recombination velocity (170 cm/s) was recorded at room temperature. These results suggest that InP nanowires are prime candidates for optoelectronic devices, particularly photovoltaic devices, without the need for surface passivation. We found that the carrier mobility is not limited by nanowire diameter but is strongly limited by the presence of planar crystallographic defects such as stacking faults in these predominantly wurtzite nanowires. These findings show the great potential of very narrow InP nanowires for electronic devices but indicate that improvements in the crystallographic uniformity of InP nanowires will be critical for future nanowire device engineering.

Taper-free and kinked germanium nanowires grown on silicon via purging and the two-temperature process.

We investigate the growth procedures for achieving taper-free and kinked germanium nanowires epitaxially grown on silicon substrates by chemical vapor deposition. Singly and multiply kinked germanium nanowires consisting of <111> segments were formed by employing a reactant gas purging process. Unlike non-epitaxial kinked nanowires, a two-temperature process is necessary to maintain the taper-free nature of segments in our kinked germanium nanowires on silicon. As an application, nanobridges formed between (111) side walls of V-grooved (100) silicon substrates have been demonstrated.

Self-healing of fractured GaAs nanowires.

In-situ deformation experiments were carried out in a transmission electron microscope to investigate the structural response of single crystal GaAs nanowires (NWs) under compression. A repeatable self-healing process was discovered in which a partially fractured GaAs NW restored its original single crystal structure immediately after an external compressive force was removed. Possible mechanisms of the self-healing process are discussed.

Characterization of semiconductor nanowires using optical tweezers.

We report on the optical trapping characteristics of InP nanowires with dimensions of 30 (±6) nm in diameter and 2-15 µm in length. We describe a method for calibrating the absolute position of individual nanowires relative to the trapping center using synchronous high-speed position sensing and acousto-optic beam switching. Through brownian dynamics we investigate effects of the laser power and polarization on trap stability, as well as length dependence and the effect of simultaneous trapping multiple nanowires.

Growth of straight InAs-on-GaAs nanowire heterostructures.

One of the main motivations for the great interest in semiconductor nanowires is the possibility of easily growing advanced heterostructures that might be difficult or even impossible to achieve in thin films. For III-V semiconductor nanowires, axial heterostructures with an interchange of the group III element typically grow straight in only one interface direction. In the case of InAs-GaAs heterostructures, straight nanowire growth has been demonstrated for growth of GaAs on top of InAs, but so far never in the other direction. In this article, we demonstrate the growth of straight axial heterostructures of InAs on top of GaAs. The heterostructure interface is sharp and we observe a dependence on growth parameters closely related to crystal structure as well as a diameter dependence on straight nanowire growth. The results are discussed by means of accurate first principles calculations of the interfacial energies. In addition, the role of the gold seed particle, the effect of its composition at different stages during growth, and its size are discussed in relation to the results observed.

Photomodulated rayleigh scattering of single semiconductor nanowires: probing electronic band structure.

The internal electronic structures of single semiconductor nanowires can be resolved using photomodulated Rayleigh scattering spectroscopy. The Rayleigh scattering from semiconductor nanowires is strongly polarization sensitive which allows a nearly background-free method for detecting only the light that is scattered from a single nanowire. While the Rayleigh scattering efficiency from a semiconductor nanowire depends on the dielectric contrast, it is relatively featureless as a function of energy. However, if the nanowire is photomodulated using a second pump laser beam, the internal electronic structure can be resolved with extremely high signal-to-noise and spectral resolution. The photomodulated Rayleigh scattering spectra can be understood theoretically as a first derivative of the scattering efficiency that results from a modulation of the band gap and depends sensitively on the nanowire diameter. Fits to spectral lineshapes provide both the band structure and the diameter of individual GaAs and InP nanowires under investigation.