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Funding Information: This work was financially supported by NanoLund, Myfab, the Swedish Research Council, the Swedish Energy Agency, and the Knut and Alice Wallenberg Foundation. Publisher Copyright: © 2021 The Authors. Published by American Chemical Society. Nanowire solar cells have the potential to reach the same efficiencies as the world-record III-V solar cells while using a fraction of the material. For solar energy harvesting, large-area nanowire solar cells have to be processed. In this work, we demonstrate the synthesis of epitaxial InP nanowire arrays on a 2 inch wafer. We define five array areas with different nanowire diameters on the same wafer. We use a photoluminescence mapper to characterize the sample optically and compare it to a homogeneously exposed reference wafer. Both steady-state and time-resolved photoluminescence maps are used to study the material's quality. From a mapping of reflectance spectra, we simultaneously extract the diameter and length of the nanowires over the full wafer. The extracted knowledge of large-scale nanowire synthesis will be crucial for the upscaling of nanowire-based solar cells, and the demonstrated wafer-scale characterization methods will be central for quality control during manufacturing.

III−V nanowire (NW) photovoltaic devices promise high efficiencies at reduced materials usage. However, research has so far focused on small devices, mostly ≤1 mm2. In this study, the upscaling potential of axial junction InP NW photovoltaic devices is investigated. Device processing was carried out on a full 2″ wafer, with device sizes up to 1 cm2, which is a significant increase from the mm-scale III−V NW photovoltaic devices published previously. The short-circuit current density of the largest 1 cm2 devices, in which 460 million NWs are contacted in parallel, is on par with smaller devices. This enables a record power generation of 6.0 mW under AM1.5 G illumination, more than one order of magnitude higher than previous III−V NW photovoltaic devices. On the other hand, the fill factor of the larger devices is lower in comparison with smaller devices, which affects the device efficiency. By use of electroluminescence mapping, resistive losses in the indium tin oxide (ITO) front contact are found to limit the fill factor of the large devices. We use combined light-beam induced current (LBIC) and photoluminescence (PL) mapping as a powerful characterization tool for NW photovoltaic devices. From the LBIC and PL maps, local defects can be identified on the fully processed devices.

Nanowires require surface passivation due to their inherent large surface to volume ratio. We investigate the effect of embedding InP nanowires in different oxides with respect to surface passivation by use of electron beam induced current measurements enabled by a nanoprobe based system inside a scanning electron microscope. The measurements reveal remote doping due to fixed charge carriers in the passivating POx/Al2O3 shell in contrast to results using SiOx. We used time-resolved photoluminescence to characterize the lifetime of charge carriers to evaluate the success of surface passivation. In addition, spatially resolved internal quantum efficiency simulations support and correlate the two applied techniques. We find that atomic-layer deposited POx/Al2O3 has the potential to passivate the surface of InP nanowires, but at the cost of inducing a field-effect on the nanowires, altering their electrostatic potential profile. The results show the importance of using complementary techniques to correctly evaluate and interpret processing related effects for optimization of nanowire-based optoelectronic devices.

Here we report on the experimental results and advanced self-consistent real device simulations revealing a fundamental insight into the non-linear optical response of n+-i-n+ InP nanowire array photoconductors to selective 980 nm excitation of 20 axially embedded InAsP quantum discs in each nanowire. The optical characteristics are interpreted in terms of a photogating mechanism that results from an electrostatic feedback from trapped charge on the electronic band structure of the nanowires, similar to the gate action in a field-effect transistor. From detailed analyses of the complex charge carrier dynamics in dark and under illumination was concluded that electrons are trapped in two acceptor states, located at 140 and 190 meV below the conduction band edge, at the interface between the nanowires and a radial insulating SiOx cap layer. The non-linear optical response was investigated at length by photocurrent measurements recorded over a wide power range. From these measurements were extracted responsivities of 250 A W-1 (gain 320)@20 nW and 0.20 A W-1 (gain 0.2)@20 mW with a detector bias of 3.5 V, in excellent agreement with the proposed two-trap model. Finally, a small signal optical AC analysis was made both experimentally and theoretically to investigate the influence of the interface traps on the detector bandwidth. While the traps limit the cut-off frequency to around 10 kHz, the maximum operating frequency of the detectors stretches into the MHz region.

Measuring the current induced by the electron beam in an electron microscope is an approach that is used to map the generation and collection of charge carriers in the presence of an internal electric field in semiconductor devices. Here, we demonstrate that EBIC measurements can be conducted simultaneously with atomic-resolution high-angle annular dark field imaging in an aberration-corrected scanning transmission electron microscopy using a GaAs p-i-n nanowire diode. We explore the effects of the significantly smaller profile of the 200 kV electron probe within the sample compared to the SEM configuration. We further demonstrate that the effects of electron beam induced point defects and surface passivation layers can be directly determined using the STEM-EBIC approach.

Nanoscale X-ray detectors could allow higher resolution in imaging and diffraction experiments than established systems but are difficult to design due to the long absorption length of X-rays. Here, we demonstrate X-ray detection in a single nanowire in which the nanowire axis is parallel to the optical axis. In this geometry, X-ray absorption can occur along the nanowire length, while the spatial resolution is limited by the diameter. We use the device to make a high-resolution 3D image of the 88 nm diameter X-ray nanofocus at the Nanomax beamline, MAX IV synchrotron, by scanning the single pixel device in different planes along the optical axis. The images reveal fine details of the beam that are unattainable with established detectors and show good agreement with ptychography.

Axially heterostructured nanowires are a promising platform for next generation electronic and optoelectronic devices. Reports based on theoretical modeling have predicted more complex strain distributions and increased critical layer thicknesses than in thin films, due to lateral strain relaxation at the surface, but the understanding of the growth and strain distributions in these complex structures is hampered by the lack of high-resolution characterization techniques. Here, we demonstrate strain mapping of an axially segmented GaInP-InP 190 nm diameter nanowire heterostructure using scanning X-ray diffraction. We systematically investigate the strain distribution and lattice tilt in three different segment lengths from 45 to 170 nm, obtaining strain maps with about 10−4 relative strain sensitivity. The experiments were performed using the 90 nm diameter nanofocus at the NanoMAX beamline, taking advantage of the high coherent flux from the first diffraction limited storage ring MAX IV. The experimental results are in good agreement with a full simulation of the experiment based on a three-dimensional (3D) finite element model. The largest segments show a complex profile, where the lateral strain relaxation at the surface leads to a dome-shaped strain distribution from the mismatched interfaces, and a change from tensile to compressive strain within a single segment. The lattice tilt maps show a cross-shaped profile with excellent qualitative and quantitative agreement with the simulations. In contrast, the shortest measured InP segment is almost fully adapted to the surrounding GaInP segments.

Using light to interact with cells is a promising way to steer cell behavior with minimal perturbation. Besides optogenetics, photovoltaic nanostructures such as nanowires can be used to interact with cells using light as a switch. Photovoltaic nanowires have, for instance, been used to stimulate neurons. However, the effects of the photovoltaic activity on cells are still poorly understood and characterized. Here, we investigate the effects of the photovoltaic activity of p-i-n nanowire arrays on A549 human lung adenocarcinoma cells. We have cultured A549 cells on top of vertical arrays of indium phosphide p-i-n nanowires (photovoltaic nanowires), with and without illumination to assess the effects of the nanowire photovoltaic activity on cells. We show that there is a higher proportion of dormant cells when the p-i-n nanowire arrays are illuminated. However, there is no difference in the proportion of dormant cells when the p-i-n nanowires are coated with oxide, which suggests that carrier injection in the cell medium (in this case, the release of electrons from the tip of the nanowires) is an important factor for modulating cell proliferation on photovoltaic nanowires. The results open up for interesting applications of photovoltaic nanowires in biomedicine, such as using them as a dormancy switch.

We demonstrate a significant improvement in the optical performance of GaAs nanowires achieved using a mixed nitrogen-hydrogen plasma which passivates surface states and reduces the rate of nonradiative recombination. This has been confirmed by time-resolved photoluminescence measurements. At room temperature, the intensity and lifetime of radiative recombination in the plasma-treated nanowires was several times greater than that of the as-grown GaAs nanowires. Low-temperature measurements corroborated these findings, revealing a dramatic increase in photoluminescence by two orders of magnitude. Photoelectron spectroscopy of plasma passivated nanowires demonstrated a yearlong stability achieved through the replacement of surface oxygen with nitrogen. Furthermore, the process removed the As0 defects observed on non-passivated nanowires which are known to impair devices. The results validate plasma as a nitridation technique suitable for nanoscale GaAs crystals. As a simple ex situ procedure with modest temperature and vacuum requirements, it represents an easy method for incorporating GaAs nanostructures into optoelectronic devices.

Nanofocused X-ray beam induced current (XBIC) is used to quantitatively map the spatially dependent carrier collection probability within single nanowires., Here it is demonstrated how nanofocused X-ray beam induced current (XBIC) can be used to quantitatively map the spatially dependent carrier collection probability within nanostructured solar cells. The photocurrent generated by a 50 nm-diameter X-ray beam was measured as a function of position, bias and flux in single p–i–n doped solar-cell nanowires. The signal gathered mostly from the middle segment decays exponentially toward the p- and n-segments, with a characteristic decay length that varies between 50 nm and 750 nm depending on the flux and the applied bias. The amplitude of the XBIC shows saturation at reverse bias, which indicates that most carriers are collected. At forward bias, the relevant condition for solar cells, the carrier collection is only efficient in a small region. Comparison with finite element modeling suggests that this is due to unintentional p-doping in the middle segment. It is expected that nanofocused XBIC could be used to investigate carrier collection in a wide range of nanostructured solar cells.

Nanowire substrates play an increasingly important role for cell cultures as an approach for hybrid bio-semiconductor junctions. We investigate Jurkat T cells and neurons from mice cultured on Al2O3 coated ordered and randomly distributed nanowires. Cell viability was examined by life/membrane staining reporting comparable viability on planar and nanowire substrates. Imaging the hybrid interface reveals a wrapping of the cell membrane around the very nanowire tip. Patch clamp recordings show similar electrophysiological responses on each type of nanowires compared to planar control substrates. We demonstrate that the morphological characteristic of the nanowire substrate plays a subordinate role which opens up the arena for a large range of nanowire substrates in a functionalized application such as stimulation or sensing.

Introduction of in situ HCl etching to an epitaxial growth process has been shown to suppress radial growth and improve the morphology and optical properties of nanowires. In this paper, we investigate the dynamics of photo-generated charge carriers in a series of indium phosphide nanowires grown with varied HCl fluxes. Time resolved photo-induced luminescence, transient absorption and time resolved terahertz spectroscopy were employed to investigate charge trapping and recombination processes in the nanowires. Since the excitation photons generate charges predominantly in less than a half length of the nanowires, we can selectively assess the charge carrier dynamics at their top and bottom. We found that the photoluminescence decay is dominated by the decay of the mobile hole population due to trapping, which is affected by the HCl etching. The hole trapping rate is in general faster at the top of the nanowires than at the bottom. In contrast, electrons remain highly mobile until they recombine non-radiatively with the trapped holes. The slowest hole trapping as well as the least efficient non-radiative recombination was recorded for etching using the HCl molar fraction of χHCl = 5.4 × 10-5.

We report on the use of a sacrificial AlAs segment to enable substrate reuse for nanowire synthesis. A silicon nitride template was deposited on a p-type GaAs substrate. Then a pattern was transferred to the substrate by nanoimprint lithography and reactive ion etching. Thermal evaporation was used to define Au seed particles. Metalorganic vapour phase epitaxy was used to grow AlAs–GaAs NWs in the vapour–liquid–solid growth mode. The yield of synthesised nanowires, compared to the number expected from the patterned template, was more than 80%. After growth, the nanowires were embedded in a polymer and mechanically removed from the parent substrate. The parent substrate was then immersed in an HCl:H2O (1:1) mixture to dissolve the remaining stub of the sacrificial AlAs segment. The pattern fidelity was preserved after peeling off the nanowires and cleaning, and the semiconductor surface was flat and ready for reuse. Au seed particles were then deposited on the substrate by use of pulse electrodeposition, which was selective to the openings in the growth template, and then nanowires were regrown. The yield of regrowth was less optimal compared to the first growth but the pattern was preserved. Our results show a promising approach to reduce the final cost of III–V nanowire based solar cells.

We present an in-depth analysis of the surface band alignment and local potential distribution of InP nanowires containing a p-n junction using scanning probe and photoelectron microscopy techniques. The depletion region is localized to a 15 nm thin surface region by scanning tunneling spectroscopy and an electronic shift of up to 0.5 eV between the n- A nd p-doped nanowire segments was observed and confirmed by Kelvin probe force microscopy. Scanning photoelectron microscopy then allowed us to measure the intrinsic chemical shift of the In 3d, In 4d, and P 2p core level spectra along the nanowire and the effect of operating the nanowire diode in forward and reverse bias on these shifts. Thanks to the high-resolution techniques utilized, we observe fluctuations in the potential and chemical energy of the surface along the nanowire in great detail, exposing the sensitive nature of nanodevices to small scale structural variations. (Less)

We report on the synthesis of vertical InP nanowire arrays on (001) InP and Si substrates using template-assisted vapour–liquid–solid growth. A thick silicon oxide layer was first deposited on the substrates. The samples were then patterned by electron beam lithography and deep dry etching through the oxide layer down to the substrate surface. Gold seed particles were subsequently deposited in the holes of the pattern by the use of pulse electrodeposition. The subsequent growth of nanowires by the vapour–liquid–solid method was guided towards the [001] direction by the patterned oxide template, and displayed a high growth yield with respect to the array of holes in the template. In order to confirm the versatility and robustness of the process, we have also demonstrated guided growth of InP nanowire p–n junctions and InP/InAs/InP nanowire heterostructures on (001) InP substrates. Our results show a promising route to monolithically integrate III–V nanowire heterostructure devices with commercially viable (001) silicon platforms.

Semiconductor nanowire (NW) solar cells with a single p-n junction have exhibited efficiency comparable to that of their planar counterparts with a substantial reduction in material consumption. Tandem geometry is a path toward the fabrication of devices with even higher efficiencies, for which a key step is the fabrication of tunnel (Esaki) diodes within NWs with the correct diameter, pitch, and material combination for maximized efficiency. InP/GaInP and GaInP/InP NW tunnel diodes with band gap combinations corresponding to high-efficiency solar energy harvesting were fabricated and their electrical characteristics and material properties were compared. Four different configurations, with respect to material composition and doping, were investigated. The NW arrays were grown with metal–organic vapor-phase epitaxy from Au particles by use of nano-imprint lithography, metal evaporation and lift-off. Electrical measurements showed that the NWs behave as tunnel diodes in both InP (bottom)/GaInP (top) and GaInP (bottom)/InP (top) configurations, exhibiting a maximum peak current density of 25 A/cm2, and maximum peak to valley current ratio of 2.5 at room temperature. The realization of NW tunnel diodes in both InP/GaInP and GaInP/InP configurations represent an opportunity for the use of NW tandem solar cells, whose efficiency is independent of the growth order of the different materials, increasing the flexibility regarding dopant incorporation polarity. [Figure not available: see fulltext.]

Ga x In(1−x)P nanowires with suitable bandgap (1.35–2.26 eV) ranging from the visible to near-infrared wavelength have great potential in optoelectronic applications. Due to the large surface-to-volume ratio of nanowires, the surface states become a pronounced factor affecting device performance. In this work, we performed a systematic study of Ga x In(1−x)P nanowires’ surface passivation, utilizing Al y In(1−y)P shells grown in situ by using a metal-organic vapor phase epitaxy system. Time-resolved photoinduced luminescence and time-resolved THz spectroscopy measurements were performed to study the nanowires’ carrier recombination processes. Compared to the bare Ga0.41In0.59P nanowires without shells, the hole and electron lifetime of the nanowires with the Al0.36In0.64P shells are found to be larger by 40 and 1.1 times, respectively, demonstrating effective surface passivation of trap states. When shells with higher Al composition were grown, both lifetimes of free holes and electrons decreased prominently. We attribute the acceleration of PL decay to an increase in the trap states’ density due to the formation of defects, including the polycrystalline and oxidized amorphous areas in these samples. Furthermore, in a separate set of samples, we varied the shell thickness. We observed that a certain shell thickness of approximately ∼20 nm is needed for efficient passivation of Ga0.31In0.69P nanowires. The photoconductivity of the sample with a shell thickness of 23 nm decays 10 times slower compared with that of the bare core nanowires. We concluded that both the hole and electron trapping and the overall charge recombination in Ga x In(1−x)P nanowires can be substantially passivated through growing an Al y In(1−y)P shell with appropriate Al composition and thickness. Therefore, we have developed an effective in situ surface passivation of Ga x In(1−x)P nanowires by use of Al y In(1−y)P shells, paving the way to high-performance Ga x In(1−x)P nanowires optoelectronic devices.

It has recently been found that anti-Stokes photoluminescence can be observed in degenerately n-doped indium phosphide nanowires, when exciting directly into the electron gas. This anti-Stokes mechanism has not been observed before and allows the study of carrier relaxation and recombination using standard photoluminescence techniques. It is important to know if this anti-Stokes photoluminescence also occurs in bulk semiconductors as well as its relation to carrier recombination and relaxation. Here we show that similar anti-Stokes photoluminescence can indeed be observed in degenerately doped bulk indium phosphide and gallium arsenide and is caused by minority carriers scattering to high momenta by phonons. We find in addition that the radiative electron-hole recombination is highly momentum-conserving and that photogenerated minority carriers recombine before relaxing to the band edge at low temperatures. These observations challenge the use of models assuming thermalization of minority carriers in the analysis of highly doped devices., Anti-Stokes luminescence - the emission of photons with higher energy than those absorbed – in nanomaterials is widely used for optoelectronic applications. Here the authors observe it in degenerately doped bulk InP and GaAs, indicating it as a more general property of direct bandgap semiconductors.

Avalanche photodetectors (APDs) are key components in optical communication systems due to their increased photocurrent gain and short response time as compared to conventional photodetectors. A detector design where the multiplication region is implemented in a large band gap material is desired to avoid detrimental Zener tunneling leakage currents, a concern otherwise in smaller band gap materials required for absorption at 1.3/1.55 μm. Self-assembled III-V semiconductor nanowires offer key advantages such as enhanced absorption due to optical resonance effects, strain-relaxed heterostructures, and compatibility with mainstream silicon technology. Here, we present electrical and optical characteristics of single InP and InP/InAsP nanowire APD structures. Temperature-dependent breakdown characteristics of p+-n-n+ InP nanowire devices were investigated first. A clear trap-induced shift in breakdown voltage was inferred from I-V measurements. An improved contact formation to the p+-InP segment was observed upon annealing, and its effect on breakdown characteristics was investigated. The band gap in the absorption region was subsequently varied from pure InP to InAsP to realize spatially separate absorption and multiplication APDs in heterostructure nanowires. In contrast to the homojunction APDs, no trap-induced shifts were observed for the heterostructure APDs. A gain of 12 was demonstrated for selective optical excitation of the InAsP segment. Additional electron-beam-induced current measurements were carried out to investigate the effect of local excitation along the nanowire on the I-V characteristics. Simulated band profiles and electric field distributions support our interpretation of the experiments. Our results provide important insight for optimization of avalanche photodetector devices based on III-V nanowires. © 2017 American Chemical Society The authors acknowledge financial support from NanoLund, the Swedish Research Council, the Swedish National Board for Industrial and Technological Development, the Swedish Foundation for Strategic Research, the Ljungberg Foundation, the Carl Trygger Foundation, and the Swedish Energy Agency. This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No. 641023 (NanoTandem) and under the Marie Sklodowska-Curie grant agreement No. 656208.

We have investigated strained GaAs-GaInP core-shell nanowires using transmission electron microscopy and nanofocused scanning X-ray diffraction. Nominally identical growth conditions for each sample were achieved by using nanoimprint lithography to create wafer-scale arrays of Au seed particles. However, we observe large individual differences, with neighboring nanowires showing either straight, bent, or twisted morphology. Using scanning X-ray diffraction, we reconstructed and quantified the bending and twisting of the nanowires in three dimensions. In one nanowire, we find that the shell lattice is tilted with respect to the core lattice, with an angle that increases from 2° at the base to 5° at the top. Furthermore, the azimuthal orientation of the tilt changes by 30° along the nanowire axis. Our results demonstrate how strained core-shell nanowire growth can lead to a rich interplay of composition, lattice mismatch, bending and lattice tilt, with additional degrees of complexity compared with thin films.

Semiconductor nanowires are versatile building blocks for optoelectronic devices, in part because nanowires offer an increased freedom in material design due to relaxed constraints on lattice matching during the epitaxial growth. This enables the growth of ternary alloy nanowires in which the bandgap is tunable over a large energy range, desirable for optoelectronic devices. However, little is known about the effects of doping in the ternary nanowire materials, a prerequisite for applications. Here we present a study of p-doping of InxGa1-xP nanowires and show that the growth dynamics are strongly affected when diethylzinc is used as a dopant precursor. Specifically, using in situ optical reflectometry and high-resolution transmission electron microscopy we show that the doping results in a smaller nanowire diameter, a more predominant zincblende crystal structure, a more Ga-rich composition, and an increased axial growth rate. We attribute these effects to changes in seed particle wetting angle and increased TMGa pyrolysis efficiency upon introducing diethylzinc. Lastly, we demonstrate degenerate p-doping levels in InxGa1-xP nanowires by the realization of an Esaki tunnel diode. Our findings provide insights into the growth dynamics of ternary alloy nanowires during doping, thus potentially enabling the realization of such nanowires with high compositional homogeneity and controlled doping for high-performance optoelectronics devices.

The search for new cancer biomarkers is essential for fundamental research, diagnostics, as well as for patient treatment and monitoring. Whereas most cancer biomarkers are biomolecules, an increasing number of studies show that mechanical cues are promising biomarker candidates. Although cell deformability has been shown to be a possible cancer biomarker, cellular forces as cancer biomarkers have been left largely unexplored. Here, we measure traction forces of cancer and normal-like cells at high spatial resolution using a robust method based on dense vertical arrays of nanowires. A force map is created using automated image analysis based on the localization of the fluorescent tips of the nanowires. We show that the force distribution and magnitude differ between MCF7 breast cancer cells and MCF10A normal-like breast epithelial cells, and that monitoring traction forces can be used to investigate the effects of anticancer drugs.

Space power systems require photovoltaics that are lightweight, efficient, reliable, and capable of operating for years or decades in space environment. Current solar panels use planar multijunction, III-V based solar cells with very high efficiency, but their specific power (power to weight ratio) is limited by the added mass of radiation shielding (e.g., coverglass) required to protect the cells from the high-energy particle radiation that occurs in space. Here, we demonstrate that III-V nanowire-array solar cells have dramatically superior radiation performance relative to planar solar cell designs and show this for multiple cell geometries and materials, including GaAs and InP. Nanowire cells exhibit damage thresholds ranging from ∼10-40 times higher than planar control solar cells when subjected to irradiation by 100-350 keV protons and 1 MeV electrons. Using Monte Carlo simulations, we show that this improvement is due in part to a reduction in the displacement density within the wires arising from their nanoscale dimensions. Radiation tolerance, combined with the efficient optical absorption and the improving performance of nanowire photovoltaics, indicates that nanowire arrays could provide a pathway to realize high-specific-power, substrate-free, III-V space solar cells with substantially reduced shielding requirements. More broadly, the exceptional reduction in radiation damage suggests that nanowire architectures may be useful in improving the radiation tolerance of other electronic and optoelectronic devices.

Electron holographic tomography was used to obtain three-dimensional reconstructions of the morphology and electrostatic potential gradient of axial GaInP/InP nanowire tunnel diodes. Crystal growth was carried out in two opposite directions: GaInP-Zn/InP-S and InP-Sn/GaInP-Zn, using Zn as the p-type dopant in the GaInP but with changes to the n-type dopant (S or Sn) in the InP. Secondary electron and electron beam-induced current images obtained using scanning electron microscopy indicated the presence of p-n junctions in both cases and current-voltage characteristics measured via lithographic contacts showed the negative differential resistance, characteristic of band-to-band tunneling, for both diodes. Electron holographic tomography measurements confirmed a short depletion width in both cases (21 ± 3 nm) but different built-in potentials, Vbi, of 1.0 V for the p-type (Zn) to n-type (S) transition, and 0.4 V for both were lower than the expected 1.5 V for these junctions if degenerately doped. Charging induced by the electron beam was evident in phase images which showed nonlinearity in the surrounding vacuum, most severe in the case of the nanowire grounded at the p-type Au contact. We attribute their lower Vbi to asymmetric secondary electron emission, beam-induced current biasing, and poor grounding contacts.

The coherence of polaritons plays a fundamental role in numerous recent experimental observations, from strong coupling to Bose-Einstein condensation, but accessing the coherence of polaritons is a difficult task due to the high energy of plasmons and excitons. However, surface phonon polaritons offer similar promises at much lower energy. Here, we demonstrate the possibility to use visible ultrafast lasers to generate and time resolve coherent surface phonon polaritons in nanowires. We show that these modes are generated through the ultrafast screening of the surface depletion field. By comparing experiments and FDTD simulations, we show that this method allows the simultaneous generation of dark and bright mode. Our observations open the way to deeper investigations of the role of coherence in the rich polariton physics.

We report on growth of InP-InAs core-shell nanowires and demonstration of the formation of single quantum structures, which show Coulomb blockade effect, over entire lengths of the nanowires. The core-shell nanowires are grown by a selective area growth technique via metal-organic vapor phase epitaxy. The as-grown core-shell nanowires are found to be of wurtzite crystals. The InP cores have a hexagonal cross section, while the InAs shell are grown preferentially on specific {1$\bar{1}$00} facets, leading to the formation of the core-shell nanowires with an overall triangular cross section. The grown core-shell nanowires are transferred on to a Si/SiO$_2$ substrate and then contacted with several narrow metal electrodes. Low-temperature transport measurements show the Coulomb-blockade effect. We analyze the measured gate capacitance and single electron charging energy of the devices and demonstrate that a quantum structure which shows the Coulomb blockade effect of a many-electron quantum dot is formed over the full length of a single core-shell nanowire and consists of the entire InAs shell in the nanowire., 12 pages, 3 figures

We report on experimental determination of the strain and bandgap of InAsP in epitaxially grown InAsP-InP core-shell nanowires. The core-shell nanowires are grown via metal-organic vapor phase epitaxy. The as-grown nanowires are characterized by transmission electron microscopy, X-ray diffraction, micro-photoluminescence ($\mu$PL) spectroscopy and micro-Raman ($\mu$-Raman) spectroscopy measurements. We observe that the core-shell nanowires are of wurtzite (WZ) crystal phase and are coherently strained, with the core and the shell having the same number of atomic planes in each nanowire. We determine the predominantly uniaxial strains formed in the core-shell nanowires along the nanowire growth axis and demonstrate that the strains can be described using an analytical expression. The bandgap energies in the strained WZ InAsP core materials are extracted from the $\mu$PL measurements of individual core-shell nanowires. The coherently strained core-shell nanowires demonstrated in this work offer the potentials for use in constructing novel optoelectronic devices and for development of piezoelectric photovoltaic devices., Comment: 18 pages, 5 figures, Supporting Information

Nanotechnology 30(50), 505703 (2019). doi:10.1088/1361-6528/ab40f1, InAs x P1−x nanowires are promising building blocks for future optoelectronic devices and nanoelectronics. Their structure may vary from nanowire to nanowire, which may influence their average optoelectronic properties. Therefore, it is highly important for their applications to know the average properties of an ensemble of the nanowires. Structural properties of the InAs x P1−x -InP core–shell nanowires were investigated using the coplanar x-ray diffraction performed at a synchrotron facility. Studies of series of symmetric and asymmetric x-ray Bragg reflections allowed us to determine the 26% ± 3% of As chemical composition in the InAs x P1−x core, core–shell relaxation, and the average tilt of the nanowires with respect to the substrate normal. Based on the x-ray diffraction, scanning, and transmission electron microscopy measurements, a model of the core–shell relaxation was proposed. Partial relaxation of the core was attributed to misfit dislocations formed at the core–shell interface and their linear density was estimated to be 3.3 ± 0.3 × 104 cm−1., Published by IOP Publ., Bristol

Ternary III–V nanowires (NWs) cover a wide range of wavelengths in the solar spectrum and would greatly benefit from being synthesized as position-controlled arrays for improved vertical yield, reproducibility, and tunable optical absorption. Here, we report on successful selective-area epitaxy of metal-particle-free vertical In x Ga1−x P NW arrays using metal–organic vapor phase epitaxy and detail their optical properties. A systematic growth study establishes the range of suitable growth parameters to obtain uniform NW growth over a large array. The optical properties of the NWs were characterized by room-temperature cathodoluminescence spectroscopy. Tunability of the emission wavelength from 870 nm to approximately 800 nm was achieved. Transmission electron microscopy and energy dispersive X-ray measurements performed on cross-section samples revealed a pure wurtzite crystal structure with very few stacking faults and a slight composition gradient along the NW growth axis.

We report an alternative pathway for p-type InP nanowire (NW) doping by diffusion of Zn species from the gas phase. The diffusion of Zn was performed in a MOVPE reactor at 350–500 °C for 5–20 min with either H2 environment or additional phosphorus in the atmosphere. In addition, Zn3P2 shells were studied as protective caps during post-diffusion annealing. This post-diffusion annealing was performed to outdiffuse and activate Zn in interstitial locations. The characterization methods included photoluminescence and single NW conductivity and carrier concentration measurements. The acquired carrier concentrations were in the order of >1017 cm−3 for NWs without post-annealing, and up to 1018 cm−3 for NWs annealed with the Zn3P2 shells. The diffused Zn caused redshift to the photoluminescence signal, and the degree of redshift depended on the diffusion process.

Nanowire based solar cells hold promise for terrestrial and space photovoltaic applications. However, to speed-up and further continue with nanowire solar cell development, quick and reliable characterization tools capable of evaluating single nanowire performance of nanowires still standing on the substrate are necessary. Here, we present the use of a light emitting diode (LED) based setup, which combined with a nanoprobe system inside a scanning electron microscope, enables on-wafer, single, nanowire solar cell optoelectronic characterization. In particular, we study the I–V characteristics of single nanowire solar cells under in situ illumination and correlate the results with those of electron beam induced current measurements. Further, the LED setup enables the study of nanowire solar cell under varied incident power. We believe that this approach will enable rapid development of single and tandem nanowire based solar cells as well as other nanowire based optoelectronic devices.

Nanowire (NW) arrays containing a top segment of GaxIn1–xP are investigated, comparing NWs grown using two different Ga precursors, trimethylgallium (TMGa) and triethylgallium (TEGa). TMGa is the precursor commonly used for the particle-assisted vapor–liquid–solid (VLS) growth of GaxIn1–xP NWs. However, it shows inefficient pyrolysis at typical NW growth conditions. The use of the alternative precursor TEGa is investigated by making a direct comparison between NWs grown using TEGa and TMGa at otherwise identical growth conditions. Growth rates, resulting NW materials composition, and time-resolved photoluminescence (TRPL) lifetimes are investigated. With increasing Ga content of the NWs, the TRPL lifetimes decrease, indicating trap states that are associated with GaP. Somewhat longer TRPL lifetimes for the samples grown using TEGa indicate a lower concentration of deep trap states. For doped NWs, it is found that the strong effect of the p-type dopant diethylzinc (DEZn) on the NW composition, observed for GaxIn1–xP NWs grown using TMGa, is absent when using TEGa. (Less)

The separation of hot carriers in semiconductors is of interest for applications such as thermovoltaic photodetection and third-generation photovoltaics. Semiconductor nanowires offer several potential advantages for effective hot-carrier separation such as: a high degree of control and flexibility in heterostructure-based band engineering, increased hot-carrier temperatures compared to bulk, and a geometry well suited for local control of light absorption. Indeed, InAs nanowires with a short InP energy barrier have been observed to produce electric power under global illumination, with an open-circuit voltage exceeding the Shockley-Queisser limit. To understand this behaviour in more detail, it is necessary to establish control over the precise location of electron-hole pair-generation in the nanowire. In this work we perform electron-beam induced current measurements with high spatial resolution, and demonstrate the role of the InP barrier in extracting energetic electrons.We interprete the results in terms of hot-carrier separation, and extract estimates of the hot carriers’ mean free path.

III−V solar cells in the nanowire geometry mighth old significant synthesis-cost and device-design advantages as compared to thin films and have shown impressive performance improvements in recent years. To continue this development there is a need for characterization techniques giving quick and reliable feedback for growth development. Further, characterization techniques which can improve understanding of the link between nanowire growth conditions, subsequent processing, and solar cell performance are desired. Here, we present the use of a nanoprobe system inside a scanning electron microscope to efficiently contact single nanowires and characterize them in terms of key parameters for solar cell performance. Specifically, we study single as-grown InP nanowires and use electron beam induced current characterization to understand the charge carrier collection properties, and dark current−voltage characteristics to understand the diode recombination characteristics. By correlating the single nanowire measurements to performance of fully processed nanowire array solar cells, we identify how the performance limiting parameters are related to growth and/or processing conditions. We use this understanding to achieve a more than 7-fold improvement in efficiency of our InP nanowire solar cells, grown from a different seed particle pattern than previously reported from our group. The best cell shows a certified efficiency of 15.0%; the highest reported value for a bottom-up synthesized InP nanowire solar cell. We believe the presented approach have significant potential to speed-up the development of nanowire solar cells, as well as other nanowire-based electronic/optoelectronic devices.

The development of photovoltaics as a serious means of producing renewable energy has accelerated greatly in the last ten years, with prices for silicon-based solar cell systems dropping dramatically in the last few years. The next great opportunity for photovoltaics following this competitiveness in prices will be to enhance the cell and panel efficiencies. It is quite generally seen that the most viable platform on which this should be realized will be as augmented silicon solar cells, in which a top cell will be combined with the silicon bottom cell in a tandem configuration, by which the efficiency can be enhanced by a factor from 20% to 50%, depending on details of the approach. In this paper, we report on the status of one such approach, namely, with a top cell comprising III-V nanowires, connected to the bottom silicon cell in a two-terminal or four-terminal configuration. Among the most important opportunities, we show that a substrate-free growth, called Aerotaxy, offers a radical reduction in the total price picture. Besides the description of the key technical approaches, we also discuss the environmental issues.

International audience; The properties of semiconductors can be controlled using doping, making it essential for electronic and optoelectronic devices. However, with shrinking device sizes it becomes increasingly difficult to quantify doping with sufficient sensitivity and spatial resolution. Here, we demonstrate how X-ray fluorescence mapping with a nanofocused beam, nano-XRF, can quantify Zn doping within in situ doped III-V nanowires, by using large area detectors and high-efficiency focusing optics. The spatial resolution is defined by the focus size to 50 nm. The detection limit of 7 ppm (2.8 X 10(17) cm(-3)), corresponding to about 150 Zn atoms in the probed volume, is bound by a background signal. In solar cell InP nanowires with a p-i-n doping profile, we use nano-XRF to observe an unintentional Zn doping of 5 x 10(17) cm(-3) in the middle segment. We investigated the dynamics of in situ Zn doping in a dedicated multisegment nanowire, revealing significantly sharper gradients after turning the Zn source off than after turning the source on. Nano-XRF could be used for quantitative mapping of a wide range of dopants in many types of nanostructures.

International audience; We demonstrate x-ray absorption fine structure spectroscopy (XAFS) detected by x-ray beam induced current (XBIC) in single n(+)i-n(+) doped nanowire devices. Spatial scans with the 65 nm diameter beam show a peak of the XBIC signal in the middle segment of the nanowire. The XBIC and the x-ray fluorescence signals were detected simultaneously as a function of the excitation energy near the Ga K absorption edge at 10.37 keV. The spectra show similar oscillations around the edge, which shows that the XBIC is limited by the primary absorption. Our results reveal the feasibility of the XBIC detection mode for the XAFS investigation in nanostructured devices.

GaxIn(1−x)P nanowire arrays are promising for various optoelectronic applications with a tunable band-gap over a wide range. In particular, they are well suited as the top cell in tandem junction solar cell devices. So far, most GaxIn(1−x)P nanowires have been synthesized by the use of trimethylgallium (TMGa). However, particle assisted nanowire growth in metal organic vapor phase epitaxy is typically carried out at relatively low temperatures, where TMGa is not fully pyrolysed. In this work, we developed the growth of GaxIn(1−x)P nanowires using triethylgallium (TEGa) as the Ga precursor, which reduced Ga precursor consumption by about five times compared to TMGa due to the lower homogeneous pyrolysis temperature of TEGa. The versatility of TEGa is shown by synthesis of high yield GaxIn(1−x)P nanowire arrays, with a material composition tunable by the group III input flows, as verified by x-ray diffraction measurements and photoluminescence characterization. The growth dynamics of GaxIn(1−x)P nanowires was assessed by varying the input growth precursor molar fractions and growth temperature, using hydrogen-chloride as in situ etchant. We observed a complex interplay between the precursors. First, trimethylindium (TMIn) inhibits Ga incorporation into the nanowires, resulting in higher In composition in the grown nanowires than in the vapor. Second, the growth rate increases with temperature, indicating a kinetically limited growth, which from nanowire effective binary volume growth rates of InP and GaP can be attributed to the synthesis of GaP in GaxIn(1−x)P. We observed that phosphine has a strong effect on the nanowire growth rate with behavior expected for a unimolecular Langmuir–Hinshelwood mechanism of pyrolysis on a catalytic surface. However, growth rates increase strongly with both TEGa and TMIn precursors as well, indicating the complexity of vapor–liquid–solid growth for ternary materials. One precursor can affect the decomposition of another, and each precursor can affect the wetting properties and catalytic activity of the metal particle. (Less)

To harvest the benefits of III–V nanowires in optoelectronic devices, the development of ternary materials with controlled doping is needed. In this work, we performed a systematic study of n-type dopant incorporation in dense In x Ga(1−x)P nanowire arrays using tetraethyl tin (TESn) and hydrogen sulfide (H2S) as dopant precursors. The morphology, crystal structure and material composition of the nanowires were characterized by use of scanning electron microscopy, transmission electron microscopy and energy dispersive x-ray analysis. To investigate the electrical properties, the nanowires were broken off from the substrate and mechanically transferred to thermally oxidized silicon substrates, after which electron beam lithography and metal evaporation were used to define electrical contacts to selected nanowires. Electrical characterization, including four-probe resistivity and Hall effect, as well as back-gated field effect measurements, is combined with photoluminescence spectroscopy to achieve a comprehensive evaluation of the carrier concentration in the doped nanowires. We measure a carrier concentration of ~1 × 1016 cm−3 in nominally intrinsic nanowires, and the maximum doping level achieved by use of TESn and H2S as dopant precursors using our parameters is measured to be ~2 × 1018 cm−3, and ~1 × 1019 cm−3, respectively (by Hall effect measurements). Hence, both TESn and H2S are suitable precursors for a wide range of n-doping levels in In x Ga(1−x)P nanowires needed for optoelectronic devices, grown via the vapor–liquid–solid mode.

The doping process in GaP core-shell nanowire pn-junctions using different precursors is evaluated by mapping the nanowires' electrostatic potential distribution by means of off-axis electron holography. Three precursors, triethyltin (TESn), ditertiarybutylselenide, and silane are investigated for n-type doping of nanowire shells; among them, TESn is shown to be the most efficient precursor. Off-axis electron holography reveals higher electrostatic potentials in the regions of nanowire cores grown by the vapor-liquid-solid (VLS) mechanism (axial growth) than the regions grown parasitically by the vapor-solid (VS) mechanism (radial growth), attributed to different incorporation efficiency between VLS and VS of unintentional p-type carbon doping originating from the trimethylgallium precursor. This study shows that off-axis electron holography of doped nanowires is unique in terms of the ability to map the electrostatic potential and thereby the active dopant distribution with high spatial resolution.

Semiconductor nanowires offer great potential for realizing broadband photodetectors that are compatible with silicon technology. However, the spectral range of such detectors has so far been limited to selected regions in the ultraviolet, visible and near infrared. Here, we report on broadband nanowire heterostructure array photodetectors exhibiting a photoresponse from the visible to long-wavelength infrared. In particular, the infrared response from 3-20 um is enabled by normal incidence excitation of intersubband transitions in low-bandgap InAsP quantum discs synthesized axially within InP nanowires. The optical characteristics are explained by the excitation of the longitudinal component of optical modes in the photonic crystal formed by the nanostructured portion of the detectors, combined with a non-symmetric potential profile of the discs resulting from synthesis. Our results provide a generalizable insight into how broadband nanowire photodetectors may be designed, and how engineered nanowire heterostructures open up new fascinating opportunities for optoelectronics.

We report on the fabrication and characterization of radial tunnel diodes based on InP(n+)/InGaAs(p+) core-shell nanowires, where the effect of Zn-dopant precursor flow on the electrical properties of the devices is evaluated. Selective and local etching of the InGaAs shell is employed to access the nanowire core in the contact process. Devices with an n+-p doping profile show normal diode rectification, whereas n+-p+ junctions exhibit typical tunnel diode characteristics with peak-to-valley current ratios up to 14 at room temperature and 100 at 4.2 K. A maximum peak current density of 28 A/cm2 and a reverse current density of 7.3 kA/cm2 at VSD = −0.5 V are extracted at room temperature after normalization with the effective junction area.

Nanowires hold great promise as tools for probing and interacting with various molecular and biological systems. Their unique geometrical properties (typically