Microscopic insights into metal diffusion and ohmic contact formation in delta-doped GaAs/(Al,Ga)As core/shell nanowires.

Semiconductor nanowires (NWs) are promising candidates for use in electronic and optoelectronic applications, offering numerous advantages over their thin film counterparts. Their performance relies heavily on the quality of the contacts to the NW, which should exhibit ohmic behavior with low resistance and should be formed in a reproducible manner. In the case of heterostructure NWs for high-mobility applications that host a two-dimensional electron gas, ohmic contacts are particularly challenging to implement since the NW core constituting the conduction channel is away from the NW surface. We investigated contact formation to modulation-doped GaAs/(Al,Ga)As core/shell NWs using scanning transmission electron microscopy, energy dispersive x-ray spectroscopy and electron tomography to correlate microstructure, diffusion profile and chemical composition of the NW contact region with the current-voltage (I-V) characteristics of the contacted NWs. Our results illustrate how diffusion, alloying and phase formation processes essential to the effective formation of ohmic contacts are more intricate than in planar layers, leading to reproducibility challenges even when the processing conditions are the same. We demonstrate that the NW geometry plays a crucial role in the creation of good contacts. Both ohmic and rectifying contacts were obtained under nominally identical processing conditions. Furthermore, the presence of Ge in the NW core, in the absence of Au and Ni, was found as the key factor leading to ohmic contacts. The analysis contributes to the current understanding of ohmic contact formation to heterostructure core/shell NWs offering pathways to enhance the reproducibility and further optimization of such NW contacts.

Axial Growth Characteristics of Optically Active InGaAs Nanowire Heterostructures for Integrated Nanophotonic Devices.

III-V semiconductor nanowire (NW) heterostructures with axial InGaAs active regions hold large potential for diverse on-chip device applications, including site-selectively integrated quantum light sources, NW lasers with high material gain, as well as resonant tunneling diodes and avalanche photodiodes. Despite various promising efforts toward high-quality single or multiple axial InGaAs heterostacks using noncatalytic growth mechanisms, the important roles of facet-dependent shape evolution, crystal defects, and the applicability to more universal growth schemes have remained elusive. Here, we report the growth of optically active InGaAs axial NW heterostructures via completely catalyst-free, selective-area molecular beam epitaxy directly on silicon (Si) using GaAs(Sb) NW arrays as tunable, high-uniformity growth templates and highlight fundamental relationships between structural, morphological, and optical properties of the InGaAs region. Structural, compositional, and 3D-tomographic characterizations affirm the desired directional growth along the NW axis with no radial growth observed. Clearly distinct luminescence from the InGaAs active region is demonstrated, where tunable array-geometry parameters and In content up to 20% are further investigated. Based on the underlying twin-induced growth mode, we further describe the facet-dependent shape and interface evolution of the InGaAs segment and its direct correlation with emission energy.

Strong Dimensional and Structural Dependencies of Hot Carrier Effects in InGaAs Nanowires: Implications for Photovoltaic Solar Cells.

III-V nanowire structures are among the promising material systems with applications in hot carrier solar cells. These nanostructures can meet the requirements for such photovoltaic devices, i.e., the suppression of thermalization loss, an efficient hot carrier transport, and enhanced photoabsorption thanks to their unique one-dimensional (1D) geometry and density-of-states. Here, we investigate the effects of spatial confinement of photogenerated hot carriers in InGaAs-InAlAs core-shell nanowires, which presents an ideal class of hot carrier solar cell materials due to its suitable electronic properties. Using steady-state photoluminescence spectroscopy, our study reveals that by increasing the degree of spatial confinement and Auger recombination, the effects of hot carriers increase, which is in good agreement with theoretical modeling. However, for thin nanowires, the temperature of hot carriers decreases as the effects of crystal disorder increase. This observation is confirmed by probing the extent of the disorder-induced Urbach tail and linked to the presence of a higher density of stacking defects in the limit of thin nanowires. These findings expand our knowledge of hot carrier thermalization in nanowires, which can be applied for designing efficient 1D hot carrier absorbers for advanced-concept photovoltaic solar cells.

Real-time thermal decomposition kinetics of GaAs nanowires and their crystal polytypes on the atomic scale.

Nanowires (NWs) offer unique opportunities for tuning the properties of III-V semiconductors by simultaneously controlling their nanoscale dimensions and switching their crystal phase between zinc-blende (ZB) and wurtzite (WZ). While much of this control has been enabled by direct, forward growth, the reverse reaction, i.e., crystal decomposition, provides very powerful means to further tailor properties towards the ultra-scaled dimensional level. Here, we use in situ transmission electron microscopy (TEM) to investigate the thermal decomposition kinetics of clean, ultrathin GaAs NWs and the role of distinctly different crystal polytypes in real-time and on the atomic scale. The whole process, from the NW growth to the decomposition, is conducted in situ without breaking vacuum to maintain pristine crystal surfaces. Radial decomposition occurs much faster for ZB- compared to WZ-phase NWs, due to the development of nano-faceted sidewall morphology and sublimation along the entire NW length. In contrast, WZ NWs form single-faceted, vertical sidewalls with decomposition proceeding only via step-flow mechanism from the NW tip. Concurrent axial decomposition is generally faster than the radial process, but is significantly faster (∼4-fold) in WZ phase, due to the absence of well-defined facets at the tip of WZ NWs. The results further show quantitatively the influence of the NW diameter on the sublimation and step-flow decomposition velocities elucidating several effects that can be exploited to fine-tune the NW dimensions.

Sb-Mediated Tuning of Growth- and Exciton Dynamics in Entirely Catalyst-Free GaAsSb Nanowires.

Vapor-liquid-solid (VLS) growth is the mainstream method in realizing advanced semiconductor nanowires (NWs), as widely applied to many III-V compounds. It is exclusively explored also for antimony (Sb) compounds, such as the relevant GaAsSb-based NW materials, although morphological inhomogeneities, phase segregation, and limitations in the supersaturation due to Sb strongly inhibit their growth dynamics. Fundamental advances are now reported here via entirely catalyst-free GaAsSb NWs, where particularly the Sb-mediated effects on the NW growth dynamics and physical properties are investigated in this novel growth regime. Remarkably, depending on GaAsSb composition and nature of the growth surface, both surfactant and anti-surfactant action is found, as seen by transitions between growth acceleration and deceleration characteristics. For threshold Sb-contents up to 3-4%, adatom diffusion lengths are increased ≈sevenfold compared to Sb-free GaAs NWs, evidencing the significant surfactant effect. Furthermore, microstructural analysis reveals unique Sb-mediated transitions in compositional structure, as well as substantial reduction in twin defect density, ≈tenfold over only small compositional range (1.5-6% Sb), exhibiting much larger dynamics as found in VLS-type GaAsSb NWs. The effect of such extended twin-free domains is corroborated by ≈threefold increases in exciton lifetime (≈4.5 ns) due to enlarged electron-hole pair separation in these phase-pure NWs.

3D Bragg Coherent Diffraction Imaging of Extended Nanowires: Defect Formation in Highly Strained InGaAs Quantum Wells.

InGaAs quantum wells embedded in GaAs nanowires can serve as compact near-infrared emitters for direct integration onto Si complementary metal oxide semiconductor technology. While the core-shell geometry in principle allows for a greater tuning of composition and emission, especially farther into the infrared, the practical limits of elastic strain accommodation in quantum wells on multifaceted nanowires have not been established. One barrier to progress is the difficulty of directly comparing the emission characteristics and the precise microstructure of a single nanowire. Here we report an approach to correlating quantum well morphology, strain, defects, and emission to understand the limits of elastic strain accommodation in nanowire quantum wells specific to their geometry. We realize full 3D Bragg coherent diffraction imaging (BCDI) of intact quantum wells on vertically oriented epitaxial nanowires, which enables direct correlation with single-nanowire photoluminescence. By growing In0.2Ga0.8As quantum wells of distinct thicknesses on different facets of the same nanowire, we identified the critical thickness at which defects are nucleated. A correlation with a traditional transmission electron microscopy analysis confirms that BCDI can image the extended structure of defects. Finite element simulations of electron and hole states explain the emission characteristics arising from strained and partially relaxed regions. This approach, imaging the 3D strain and microstructure of intact nanowire core-shell structures with application-relevant dimensions, can aid the development of predictive models that enable the design of new compact infrared emitters.

Heat-Mode Excitation in a Proximity Superconductor.

Mesoscopic superconductivity deals with various quasiparticle excitation modes, only one of them-the charge-mode-being directly accessible for conductance measurements due to the imbalance in populations of quasi-electron and quasihole excitation branches. Other modes carrying heat or even spin, valley etc. currents populate the branches equally and are charge-neutral, which makes them much harder to control. This noticeable gap in the experimental studies of mesoscopic non-equilibrium superconductivity can be filled by going beyond the conventional DC transport measurements and exploiting spontaneous current fluctuations. Here, we perform such an experiment and investigate the transport of heat in an open hybrid device based on a superconductor proximitized InAs nanowire. Using shot noise measurements, we investigate sub-gap Andreev heat guiding along the superconducting interface and fully characterize it in terms of the thermal conductance on the order of Gth∼e2/h, tunable by a back gate voltage. Understanding of the heat-mode also uncovers its implicit signatures in the non-local charge transport. Our experiments open a direct pathway to probe generic charge-neutral excitations in superconducting hybrids.

Sub-nanosecond acousto-electric carrier redistribution dynamics and transport in polytypic GaAs nanowires.

The authors report on a combined structural, optical and acousto-electric study of polytypic GaAs nanowires. Two types of nanowires with different zincblende and wurtzite crystal phase mixing are identified by transmission electron microscopy and photoluminescence spectroscopy. The nanowires exhibit characteristic recombination channels which are assigned to different types of spatially direct recombination (electron and hole within the same crystal phase segment) and spatially indirect recombination (electron and holes localized in different segments). Contact-free acousto-optoelectric spectroscopy is employed to resolve spatiotemporal charge carrier dynamics between different recombination channels induced by a piezoelectric surface acoustic wave. The observed suppression of the emission and its dynamic temporal modulation shows unambiguous fingerprints of the local bandedge variations induced by the crystal phase mixing. A nanowire, which exhibits a variation from a near-pristine zinc blende crystal structure to a highly mixed crystal phase, shows a clear dependence on the propagation direction of the acoustic wave. In contrast, no pronounced directionality is found for a nanowire with an extended near-pristine zincblende segment. The experimental findings are corroborated by solving the drift and diffusion equations of electrons and holes induced by the surface acoustic wave. The key characteristics observed in our experimental data are well reproduced in the numerical simulations by assuming two general bandedge modulations and realistic parameters for the bandedge discontinuities and transport mobilities of electrons and holes. This evidences that even all relevant physical processes are accounted for in the model.

Ultrafast electron cycloids driven by the transverse spin of a surface acoustic wave.

Spin-momentum locking is a universal wave phenomenon promising for applications in electronics and photonics. In acoustics, Lord Rayleigh showed that surface acoustic waves exhibit a characteristic elliptical particle motion strikingly similar to spin-momentum locking. Although these waves have become one of the few phononic technologies of industrial relevance, the observation of their transverse spin remained an open challenge. Here, we observe the full spin dynamics by detecting ultrafast electron cycloids driven by the gyrating electric field produced by a surface acoustic wave propagating on a slab of lithium niobate. A tubular quantum well wrapped around a nanowire serves as an ultrafast sensor tracking the full cyclic motion of electrons. Our acousto-optoelectrical approach opens previously unknown directions in the merged fields of nanoacoustics, nanophotonics, and nanoelectronics for future exploration.

Growth dynamics and compositional structure in periodic InAsSb nanowire arrays on Si (111) grown by selective area molecular beam epitaxy.

We report a comprehensive study of the growth dynamics in highly periodic, composition tunable InAsSb nanowire (NW) arrays using catalyst-free selective area molecular beam epitaxy. Employing periodically patterned SiO2-masks on Si (111) with various mask opening sizes (20-150 nm) and pitches (0.25-2 µm), high NW yield of >90% (irrespective of the InAsSb alloy composition) is realized by the creation of an As-terminated 1 × 1-Si(111) surface prior to NW nucleation. While the NW aspect ratio decreases continually with increasing Sb content (x Sb from 0% to 30%), we find a remarkable dependence of the aspect ratio on the mask opening size yielding up to ∼8-fold increase for openings decreasing from 150 to 20 nm. The effects of the interwire separation (pitch) on the NW aspect ratio are strongest for pure InAs NWs and gradually vanish for increasing Sb content, suggesting that growth of InAsSb NW arrays is governed by an In surface diffusion limited regime even for the smallest investigated pitches. Compositional analysis using high-resolution x-ray diffraction reveals a substantial impact of the pitch on the alloy composition in homogeneous InAsSb NW arrays, leading to much larger x Sb as the pitch increases due to decreasing competition for Sb adatoms. Scanning transmission electron microscopy and associated energy-dispersive x-ray spectroscopy performed on the cross-sections of individual NWs reveal an interesting growth-axis dependent core-shell like structure with a discontinuous few-nm thick Sb-deficient coaxial boundary layer and six Sb-deficient corner bands. Further analysis evidences the presence of a nanoscale facet at the truncation of the (111)B growth front and {1-10} sidewall surfaces that is found responsible for the formation of the characteristic core-shell structure.

Contact Architecture Controls Conductance in Monolayer Devices.

The architecture of electrically contacting the self-assembled monolayer (SAM) of an organophosphonate has a profound effect on a device where the SAM serves as an intermolecular conductive channel in the plane of the substrate. Nanotransfer printing (nTP) enabled the construction of top-contact and bottom-contact architectures; contacts were composed of 13 nm thin metal films that were separated by a ca. 20 nm gap. Top-contact devices were fabricated by assembling the SAM across the entire surface of an insulating substrate and then applying the patterned metallic electrodes by nTP; bottom-contact ones were fabricated by nTP of the electrode pattern onto the substrate before the SAM was grown in the patterned nanogaps. SAMs were prepared from (9,10-di(naphthalen-2-yl)anthracen-2-yl)phosphonate; here, the naphthyl groups extend laterally from the anthracenylphosphonate backbone. Significantly, top-contact devices supported current that was about 3 orders of magnitude greater than that for comparable bottom-contact devices and that was at least 100,000 times greater than for a control device devoid of a SAM (at 0.5 V bias). These large differences in conductance between top- and bottom-contact architectures are discussed in consideration of differential contact-to-SAM geometries and, hence, resistances.

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.

Dislocation-induced thermal transport anisotropy in single-crystal group-III nitride films.

Dislocations, one-dimensional lattice imperfections, are common to technologically important materials such as III-V semiconductors, and adversely affect heat dissipation in, for example, nitride-based high-power electronic devices. For decades, conventional nonlinear elasticity models have predicted that this thermal resistance is only appreciable when the heat flux is perpendicular to the dislocations. However, this dislocation-induced anisotropic thermal transport has yet to be seen experimentally. Using time-domain thermoreflectance, we measure strong thermal transport anisotropy governed by highly oriented threading dislocation arrays throughout micrometre-thick, single-crystal indium nitride films. We find that the cross-plane thermal conductivity is almost tenfold higher than the in-plane thermal conductivity at 80 K when the dislocation density is ~3 × 1010 cm-2. This large anisotropy is not predicted by conventional models. With enhanced understanding of dislocation-phonon interactions, our results may allow the tailoring of anisotropic thermal transport with line defects, and could facilitate methods for directed heat dissipation in the thermal management of diverse device applications.

Connecting Composition-Driven Faceting with Facet-Driven Composition Modulation in GaAs-AlGaAs Core-Shell Nanowires.

Ternary III-V alloys of tunable bandgap are a foundation for engineering advanced optoelectronic devices based on quantum-confined structures including quantum wells, nanowires, and dots. In this context, core-shell nanowires provide useful geometric degrees of freedom in heterostructure design, but alloy segregation is frequently observed in epitaxial shells even in the absence of interface strain. High-resolution scanning transmission electron microscopy and laser-assisted atom probe tomography were used to investigate the driving forces of segregation in nonplanar GaAs-AlGaAs core-shell nanowires. Growth-temperature-dependent studies of Al-rich regions growing on radial {112} nanofacets suggest that facet-dependent bonding preferences drive the enrichment, rather than kinetically limited diffusion. Observations of the distinct interface faceting when pure AlAs is grown on GaAs confirm the preferential bonding of Al on {112} facets over {110} facets, explaining the decomposition behavior. Furthermore, three-dimensional composition profiles generated by atom probe tomography reveal the presence of Al-rich nanorings perpendicular to the growth direction; correlated electron microscopy shows that short zincblende insertions in a nanowire segment with predominantly wurtzite structure are enriched in Al, demonstrating that crystal phase engineering can be used to modulate composition. The findings suggest strategies to limit alloy decomposition and promote new geometries of quantum confined structures.

He-Ion Microscopy as a High-Resolution Probe for Complex Quantum Heterostructures in Core-Shell Nanowires.

Core-shell semiconductor nanowires (NW) with internal quantum heterostructures are amongst the most complex nanostructured materials to be explored for assessing the ultimate capabilities of diverse ultrahigh-resolution imaging techniques. To probe the structure and composition of these materials in their native environment with minimal damage and sample preparation calls for high-resolution electron or ion microscopy methods, which have not yet been tested on such classes of ultrasmall quantum nanostructures. Here, we demonstrate that scanning helium ion microscopy (SHeIM) provides a powerful and straightforward method to map quantum heterostructures embedded in complex III-V semiconductor NWs with unique material contrast at ∼1 nm resolution. By probing the cross sections of GaAs-Al(Ga)As core-shell NWs with coaxial GaAs quantum wells as well as short-period GaAs/AlAs superlattice (SL) structures in the shell, the Al-rich and Ga-rich layers are accurately discriminated by their image contrast in excellent agreement with correlated, yet destructive, scanning transmission electron microscopy and atom probe tomography analysis. Most interestingly, quantitative He-ion dose-dependent SHeIM analysis of the ternary AlGaAs shell layers and of compositionally nonuniform GaAs/AlAs SLs reveals distinct alloy composition fluctuations in the form of Al-rich clusters with size distributions between ∼1-10 nm. In the GaAs/AlAs SLs the alloy clustering vanishes with increasing SL-period (>5 nm-GaAs/4 nm-AlAs), providing insights into critical size dimensions for atomic intermixing effects in short-period SLs within a NW geometry. The straightforward SHeIM technique therefore provides unique benefits in imaging the tiniest nanoscale features in topography, structure and composition of a multitude of diverse complex semiconductor nanostructures.

Correlated Chemical and Electrically Active Dopant Analysis in Catalyst-Free Si-Doped InAs Nanowires.

Direct correlations between dopant incorporation, distribution, and their electrical activity in semiconductor nanowires (NW) are difficult to access and require a combination of advanced nanometrology methods. Here, we present a comprehensive investigation of the chemical and electrically active dopant concentrations in n-type Si-doped InAs NW grown by catalyst-free molecular beam epitaxy using various complementary techniques. N-type carrier concentrations are determined by Seebeck effect measurements and four-terminal NW field-effect transistor characterization and compared with the Si dopant distribution analyzed by local electrode atom probe tomography. With increased dopant supply, a distinct saturation of the free carrier concentration is observed in the mid-1018 cm-3 range. This behavior coincides with the incorporated Si dopant concentrations in the bulk part of the NW, suggesting the absence of compensation effects. Importantly, excess Si dopants with very high concentrations (>1020 cm-3) segregate at the NW sidewall surfaces, which confirms recent first-principles calculations and results in modifications of the surface electronic properties that are sensitively probed by field-effect measurements. These findings are expected to be relevant also for doping studies of other noncatalytic III-V NW systems.

Measuring Three-Dimensional Strain and Structural Defects in a Single InGaAs Nanowire Using Coherent X-ray Multiangle Bragg Projection Ptychography.

III-As nanowires are candidates for near-infrared light emitters and detectors that can be directly integrated onto silicon. However, nanoscale to microscale variations in structure, composition, and strain within a given nanowire, as well as variations between nanowires, pose challenges to correlating microstructure with device performance. In this work, we utilize coherent nanofocused X-rays to characterize stacking defects and strain in a single InGaAs nanowire supported on Si. By reconstructing diffraction patterns from the 21̅1̅0 Bragg peak, we show that the lattice orientation varies along the length of the wire, while the strain field along the cross-section is largely unaffected, leaving the band structure unperturbed. Diffraction patterns from the 011̅0 Bragg peak are reproducibly reconstructed to create three-dimensional images of stacking defects and associated lattice strains, revealing sharp planar boundaries between different crystal phases of wurtzite (WZ) structure that contribute to charge carrier scattering. Phase retrieval is made possible by developing multiangle Bragg projection ptychography (maBPP) to accommodate coherent nanodiffraction patterns measured at arbitrary overlapping positions at multiple angles about a Bragg peak, eliminating the need for scan registration at different angles. The penetrating nature of X-ray radiation, together with the relaxed constraints of maBPP, will enable the in operando imaging of nanowire devices.

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.