Quantum-Confinement-Enhanced Thermoelectric Properties in Modulation-Doped GaAs-AlGaAs Core-Shell Nanowires.

Nanowires (NWs) hold great potential in advanced thermoelectrics due to their reduced dimensions and low-dimensional electronic character. However, unfavorable links between electrical and thermal conductivity in state-of-the-art unpassivated NWs have, so far, prevented the full exploitation of their distinct advantages. A promising model system for a surface-passivated one-dimensional (1D)-quantum confined NW thermoelectric is developed that enables simultaneously the observation of enhanced thermopower via quantum oscillations in the thermoelectric transport and a strong reduction in thermal conductivity induced by the core-shell heterostructure. High-mobility modulation-doped GaAs/AlGaAs core-shell NWs with thin (sub-40 nm) GaAs NW core channel are employed, where the electrical and thermoelectric transport is characterized on the same exact 1D-channel. 1D-sub-band transport at low temperature is verified by a discrete stepwise increase in the conductance, which coincided with strong oscillations in the corresponding Seebeck voltage that decay with increasing sub-band number. Peak Seebeck coefficients as high as ≈65-85 µV K-1 are observed for the lowest sub-bands, resulting in equivalent thermopower of S2 σ ≈ 60 µW m-1 K-2 and S2 G ≈ 0.06 pW K-2 within a single sub-band. Remarkably, these core-shell NW heterostructures also exhibit thermal conductivities as low as ≈3 W m-1 K-1 , about one order of magnitude lower than state-of-the-art unpassivated GaAs NWs.

Breakdown of Corner States and Carrier Localization by Monolayer Fluctuations in Radial Nanowire Quantum Wells.

We report a comprehensive study of the impact of the structural properties in radial GaAs-Al0.3Ga0.7As nanowire-quantum well heterostructures on the optical recombination dynamics and electrical transport properties, emphasizing particularly the role of the commonly observed variations of the quantum well thickness at different facets. Typical thickness fluctuations of the radial quantum well observed by transmission electron microscopy lead to pronounced localization. Our optical data exhibit clear spectral shifts and a multipeak structure of the emission for such asymmetric ring structures resulting from spatially separated, yet interconnected quantum well systems. Charge carrier dynamics induced by a surface acoustic wave are resolved and prove efficient carrier exchange on native, subnanosecond time scales within the heterostructure. Experimental findings are corroborated by theoretical modeling, which unambiguously show that electrons and holes localize on facets where the quantum well is the thickest and that even minute deviations of the perfect hexagonal shape strongly perturb the commonly assumed 6-fold symmetric ground state.

Quantum Transport and Sub-Band Structure of Modulation-Doped GaAs/AlAs Core-Superlattice Nanowires.

Modulation-doped III-V semiconductor nanowire (NW) heterostructures have recently emerged as promising candidates to host high-mobility electron channels for future high-frequency, low-energy transistor technologies. The one-dimensional geometry of NWs also makes them attractive for studying quantum confinement effects. Here, we report correlated investigations into the discrete electronic sub-band structure of confined electrons in the channel of Si δ-doped GaAs-GaAs/AlAs core-superlattice NW heterostructures and the associated signatures in low-temperature transport. On the basis of accurate structural and dopant analysis using scanning transmission electron microscopy and atom probe tomography, we calculated the sub-band structure of electrons confined in the NW core and employ a labeling system inspired by atomic orbital notation. Electron transport measurements on top-gated NW transistors at cryogenic temperatures revealed signatures consistent with the depopulation of the quasi-one-dimensional sub-bands, as well as confinement in zero-dimensional-like states due to an impurity-defined background disorder potential. These findings are instructive toward reaching the ballistic transport regime in GaAs-AlGaAs based NW systems.

Direct Measurements of Fermi Level Pinning at the Surface of Intrinsically n-Type InGaAs Nanowires.

Surface effects strongly dominate the intrinsic properties of semiconductor nanowires (NWs), an observation that is commonly attributed to the presence of surface states and their modification of the electronic band structure. Although the effects of the exposed, bare NW surface have been widely studied with respect to charge carrier transport and optical properties, the underlying electronic band structure, Fermi level pinning, and surface band bending profiles are not well explored. Here, we directly and quantitatively assess the Fermi level pinning at the surfaces of composition-tunable, intrinsically n-type InGaAs NWs, as one of the prominent, technologically most relevant NW systems, by using correlated photoluminescence (PL) and X-ray photoemission spectroscopy (XPS). From the PL spectral response, we reveal two dominant radiative recombination pathways, that is, direct near-band edge transitions and red-shifted, spatially indirect transitions induced by surface band bending. The separation of their relative transition energies changes with alloy composition by up to more than ∼40 meV and represent a direct measure for the amount of surface band bending. We further extract quantitatively the Fermi level to surface valence band maximum separation using XPS, and directly verify a composition-dependent transition from downward to upward band bending (surface electron accumulation to depletion) with increasing Ga-content x(Ga) at a crossover near x(Ga) ∼ 0.2. Core level spectra further demonstrate the nature of extrinsic surface states being caused by In-rich suboxides arising from the native oxide layer at the InGaAs NW surface.

Crystal Phase Quantum Dots in the Ultrathin Core of GaAs-AlGaAs Core-Shell Nanowires.

Semiconductor quantum dots embedded in nanowires (NW-QDs) can be used as efficient sources of nonclassical light with ultrahigh brightness and indistinguishability, needed for photonic quantum information technologies. Although most NW-QDs studied so far focus on heterostructure-type QDs that provide an effective electronic confinement potential using chemically distinct regions with dissimilar electronic structure, homostructure NWs can localize excitons at crystal phase defects in leading to NW-QDs. Here, we optically investigate QD emitters embedded in GaAs-AlGaAs core-shell NWs, where the excitons are confined in an ultrathin-diameter NW core and localized along the axis of the NW core at wurtzite (WZ)/zincblende (ZB) crystal phase defects. Photoluminescence (PL)-excitation measurements performed on the QD-emission reveal sharp resonances arising from excited electronic states of the axial confinement potential. The QD-like nature of the emissive centers are suggested by the observation of a narrow PL line width, as low as ~300 µeV, and confirmed by the observation of clear photon antibunching in autocorrelation measurements. Most interestingly, time-resolved PL measurements reveal a very short radiative lifetime <1 ns, indicative of a transition from a type-II to type-I band alignment of the WZ/ZB crystal interface in GaAs due to the strong quantum confinement in the ultrathin NW core.

Photocurrents in a Single InAs Nanowire/Silicon Heterojunction.

We investigate the optoelectronic properties of single indium arsenide nanowires, which are grown vertically on p-doped silicon substrates. We apply a scanning photocurrent microscopy to study the optoelectronic properties of the single heterojunctions. The measured photocurrent characteristics are consistent with an excess charge carrier transport through midgap trap states, which form at the Si/InAs heterojunctions. Namely, the trap states add an additional transport path across a heterojunction, and the charge of the defects changes the band bending at the junction. The bending gives rise to a photovoltaic effect at a small bias voltage. In addition, we observe a photoconductance effect within the InAs nanowires at large biases.

Alloy Fluctuations Act as Quantum Dot-like Emitters in GaAs-AlGaAs Core-Shell Nanowires.

GaAs-AlxGa1-xAs (AlGaAs) core-shell nanowires show great promise for nanoscale electronic and optoelectronic devices, but the application of these nonplanar heterostructures in devices requires improved understanding and control of nanoscale alloy composition and interfaces. Multiple researchers have observed sharp emission lines of unknown origin below the AlGaAs band edge in photoluminescence (PL) spectra of core-shell nanowires; point defects, alloy composition fluctuations, and self-assembled quantum dots have been put forward as candidate structures. Here we employ laser-assisted atom probe tomography to reveal structural and compositional features that give rise to the sharp PL emission spectra. Nanoscale ellipsoidal Ga-enriched clusters resulting from random composition fluctuations are identified in the AlGaAs shell, and their compositions, size distributions, and interface characteristics are analyzed. Simulations of exciton transition energies in ellipsoidal quantum dots are used to relate the Ga nanocluster distribution with the distribution of sharp PL emission lines. We conclude that the Ga rich clusters can act as discrete emitters provided that the major diameter is ≥4 nm. Smaller clusters are under-represented in the PL spectrum, and spectral lines of larger clusters are broadened, due to quantum tunneling between clusters.

Lattice-Matched InGaAs-InAlAs Core-Shell Nanowires with Improved Luminescence and Photoresponse Properties.

Core-shell nanowires (NW) have become very prominent systems for band engineered NW heterostructures that effectively suppress detrimental surface states and improve performance of related devices. This concept is particularly attractive for material systems with high intrinsic surface state densities, such as the low-bandgap In-containing group-III arsenides, however selection of inappropriate, lattice-mismatched shell materials have frequently caused undesired strain accumulation, defect formation, and modifications of the electronic band structure. Here, we demonstrate the realization of closely lattice-matched radial InGaAs-InAlAs core-shell NWs tunable over large compositional ranges [x(Ga)∼y(Al) = 0.2-0.65] via completely catalyst-free selective-area molecular beam epitaxy. On the basis of high-resolution X-ray reciprocal space maps the strain in the NW core is found to be insignificant (ε < 0.1%), which is further reflected by the absence of strain-induced spectral shifts in luminescence spectra and nearly unmodified band structure. Remarkably, the lattice-matched InAlAs shell strongly enhances the optical efficiency by up to 2 orders of magnitude, where the efficiency enhancement scales directly with increasing band offset as both Ga- and Al-contents increase. Ultimately, we fabricated vertical InGaAs-InAlAs NW/Si photovoltaic cells and show that the enhanced internal quantum efficiency is directly translated to an energy conversion efficiency that is ∼3-4 times larger as compared to an unpassivated cell. These results highlight the promising performance of lattice-matched III-V core-shell NW heterostructures with significant impact on future development of related nanophotonic and electronic devices.

Tunable quantum confinement in ultrathin, optically active semiconductor nanowires via reverse-reaction growth.

A unique growth scheme is demonstrated to realize ultrathin GaAs nanowires on Si with sizes down to the sub-10 nm regime. While this scheme preserves the bulk-like crystal properties, correlated optical experiments reveal huge blueshifted photo-luminescence (up to ≈100 meV) with decreasing nanowire cross-section, demonstrating very strong quantum confinement effects.

Valence band splitting in wurtzite InGaAs nanoneedles studied by photoluminescence excitation spectroscopy.

We use low-temperature microphotoluminescence and photoluminescence excitation spectroscopy to measure the valence band parameters of single wurtzite InGaAs nanoneedles. The effective indium composition is measured by means of polarization-dependent Raman spectroscopy. We find that the heavy-hole and light-hole splitting is ∼95 meV at 10 K and the Stokes shift is in the range of 35-55 meV. These findings provide important insight in the band structure of wurtzite InGaAs that could be used for future bandgap engineering.

Cubic Rashba spin-orbit interaction of a two-dimensional hole gas in a strained-Ge/SiGe quantum well.

The spin-orbit interaction (SOI) of a two-dimensional hole gas in the inversion symmetric semiconductor Ge is studied in a strained-Ge/SiGe quantum well structure. We observe weak antilocalization (WAL) in the magnetoconductivity measurement, revealing that the WAL feature can be fully described by the k-cubic Rashba SOI theory. Furthermore, we demonstrate electric field control of the Rashba SOI. Our findings reveal that the heavy hole (HH) in strained Ge is a purely cubic Rashba system, which is consistent with the spin angular momentum m(j) = ± 3/2 nature of the HH wave function.

Dynamic acoustic control of individual optically active quantum dot-like emission centers in heterostructure nanowires.

We probe and control the optical properties of emission centers forming in radial heterostructure GaAs-Al0.3Ga0.7As nanowires and show that these emitters, located in Al0.3Ga0.7As layers, can exhibit quantum-dot like characteristics. We employ a radio frequency surface acoustic wave to dynamically control their emission energy, and occupancy state on a nanosecond time scale. In the spectral oscillations, we identify unambiguous signatures arising from both the mechanical and electrical component of the surface acoustic wave. In addition, different emission lines of a single emission center exhibit pronounced anticorrelated intensity oscillations during the acoustic cycle. These arise from a dynamically triggered carrier extraction out of the emission center to a continuum in the radial heterostructure. Using finite element modeling and Wentzel-Kramers-Brillouin theory we identify quantum tunneling as the underlying mechanism. These simulation results quantitatively reproduce the observed switching and show that in our systems these emission centers are spatially separated from the continuum by >10.5 nm.

Pressure dependence of Raman spectrum in InAs nanowires.

We report on a Raman scattering experiment under high pressure on InAs nanowires with mainly wurtzite crystal structure. The dependence of the phonon modes on applied pressure due to the modification of the lattice parameters has been determined along with the transverse dynamical charge. Contrary to bulk InAs, no structural transition to rock salt phase has been observed in the investigated pressure range, while an anomalous behavior of the full-width at half-maximum has been noted. Our data suggest that wurtzite InAs NWs go through a tetragonal intermediate phase. Furthermore, the resonance profile of the phonon modes as a function of the applied pressure has been investigated, giving insights into the band structure of wurtzite InAs.

Lasing from individual GaAs-AlGaAs core-shell nanowires up to room temperature.

Semiconductor nanowires are widely considered to be the next frontier in the drive towards ultra-small, highly efficient coherent light sources. While NW lasers in the visible and ultraviolet have been widely demonstrated, the major role of surface and Auger recombination has hindered their development in the near infrared. Here we report infrared lasing up to room temperature from individual core-shell GaAs-AlGaAs nanowires. When subject to pulsed optical excitation, NWs exhibit lasing, characterized by single-mode emission at 10 K with a linewidth <60 GHz. The major role of non-radiative surface recombination is obviated by the presence of an AlGaAs shell around the GaAs-active region. Remarkably low threshold pump power densities down to ~760 W cm(-2) are observed at 10 K, with a characteristic temperature of T(0)=109±12 K and lasing operation up to room temperature. Our results show that, by carefully designing the materials composition profile, high-performance infrared NW lasers can be realised using III/V semiconductors.

High mobility one- and two-dimensional electron systems in nanowire-based quantum heterostructures.

Free-standing semiconductor nanowires in combination with advanced gate-architectures hold an exceptional promise as miniaturized building blocks in future integrated circuits. However, semiconductor nanowires are often corrupted by an increased number of close-by surface states, which are detrimental with respect to their optical and electronic properties. This conceptual challenge hampers their potentials in high-speed electronics and therefore new concepts are needed in order to enhance carrier mobilities. We have introduced a novel type of core-shell nanowire heterostructures that incorporate modulation or remote doping and hence may lead to high-mobility electrons. We demonstrate the validity of such concepts using inelastic light scattering to study single modulation-doped GaAs/Al0.16Ga0.84As core-multishell nanowires grown on silicon. We conclude from a detailed experimental study and theoretical analysis of the observed spin and charge density fluctuations that one- and two-dimensional electron channels are formed in a GaAs coaxial quantum well spatially separated from the donor ions. A total carrier density of about 3 × 10(7) cm(-1) and an electron mobility in the order of 50,000 cm(2)/(V s) are estimated. Spatial mappings of individual GaAs/Al0.16Ga0.84As core-multishell nanowires show inhomogeneous properties along the wires probably related to structural defects. The first demonstration of such unambiguous 1D- and 2D-electron channels and the respective charge carrier properties in these advanced nanowire-based quantum heterostructures is the basis for various novel nanoelectronic and photonic devices.

Enhanced luminescence properties of InAs-InAsP core-shell nanowires.

Utilizing narrow band gap nanowire (NW) materials to extend nanophotonic applications to the mid-infrared spectral region (>2-3 µm) is highly attractive, however, progress has been seriously hampered due to their poor radiative efficiencies arising from nonradiative surface and Auger recombination. Here, we demonstrate up to ~ 10(2) times enhancements of the emission intensities from InAs NWs by growing an InAsP shell to produce core-shell NWs. By systematically varying the thickness and phosphorus (P)-content of the InAsP shell, we demonstrate the ability to further tune the emission energy via large strain-induced peak shifts that already exceed >100 meV at comparatively low fractional P-contents. Increasing the P-content is found to give rise to additional line width broadening due to asymmetric shell growth generated by a unique transition from {110}- to {112}-sidewall growth as confirmed by cross-sectional scanning transmission electron microscopy. The results also elucidate the detrimental effects of plastic strain relaxation on the emission characteristics, particularly in core-shell structures with very high P-content and shell thickness. Overall, our findings highlight that enhanced mid-infrared emission efficiencies with effective carrier confinement and suppression of nonradiative recombination are highly sensitive to the quality of the InAs-InAsP core-shell interface.

E(1)(A) electronic band gap in wurtzite InAs nanowires studied by resonant Raman scattering.

We report on resonant Raman experiments carried out on wurtzite InAs nanowires. Resonant conditions have been obtained by tuning either the excitation energy or the band gap through external high pressure at fixed excitation energy. A complete azimuthal study of the Raman spectra with two laser excitation lines (2.41 and 1.92 eV) has also been performed on a single wire. The measured E2(H) mode resonance indicates that the E1(A) gap is about 2.4 eV, which is considerably reduced with respect to the zinc-blende InAs E1 gap. These findings confirm recent theoretical calculations of crystal phase induced bandstructure modifications.

Spontaneous alloy composition ordering in GaAs-AlGaAs core-shell nanowires.

By employing various high-resolution metrology techniques we directly probe the material composition profile within GaAs-Al0.3Ga0.7As core-shell nanowires grown by molecular beam epitaxy on silicon. Micro Raman measurements performed along the entire (>10 µm) length of the [111]-oriented nanowires reveal excellent average compositional homogeneity of the nominally Al0.3Ga0.7As shell. In strong contrast, along the radial direction cross-sectional scanning transmission electron microscopy and associated chemical analysis reveal rich structure in the AlGaAs alloy composition due to interface segregation, nanofaceting, and local alloy fluctuations. Most strikingly, we observe a 6-fold Al-rich substructure along the corners of the hexagonal AlGaAs shell where the Al-content is up to x ~ 0.6, a factor of 2 larger than the body of the AlGaAs shell. This is associated with facet-dependent capillarity diffusion due to the nonplanarity of shell growth. A modulation of the Al-content is also found along the radial [110] growth directions of the AlGaAs shell. Besides the ~10(3)-fold enhancement of the photoluminescence yield due to inhibition of nonradiative surface recombination, the AlGaAs shell gives rise to a broadened band of sharp-line luminescence features extending ~150-30 meV below the band gap of Al0.3Ga0.7As. These features are attributed to deep level defects under influence of the observed local alloy fluctuations in the shell.

Time-resolved photoinduced thermoelectric and transport currents in GaAs nanowires.

In order to clarify the temporal interplay of the different photocurrent mechanisms occurring in single GaAs nanowire based circuits, we introduce an on-chip photocurrent pump-probe spectroscopy with a picosecond time resolution. We identify photoinduced thermoelectric, displacement, and carrier lifetime limited currents as well as the transport of photogenerated holes to the electrodes. Moreover, we show that the time-resolved photocurrent spectroscopy can be used to investigate the drift velocity of photogenerated carriers in semiconducting nanowires. Hereby, our results are relevant for nanowire-based optoelectronic and photovoltaic applications.