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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.

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.

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.

Radiation hard thin-film solar cell technologies are necessary in order to achieve a step forward in the specific power of solar arrays for space applications. In this article, we analyze the degradation of nanowire (NW) solar cells under high energy particles. GaAs NW solar cells have been irradiated with protons of 100 and 350 keV at different fluences. The radiation hardness of the NW solar cells in all the cases is remarkable in comparison with GaAs planar solar cells and prior literature. Design guidelines to optimize the specific power of NW solar cells for space applications by jointly increasing their efficiency and radiation hardness are presented.

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.

High-performance photodetectors operating in the near-infrared (0.75-1.4 μm) and short-wave infrared (1.4-3.0 μm) portion of the electromagnetic spectrum are key components in many optical systems. Here, we report on a combined experimental and theoretical study of square millimeter array infrared photodetectors comprising 3 million n+-i-n+ InP nanowires grown by MOVPE from periodically ordered Au seed particles. The nominal i-segment, comprising 20 InAs0.40P0.60 quantum discs, was grown by use of an optimized Zn doping to compensate the nonintentional n-doping. The photodetectors exhibit bias- and power-dependent responsivities reaching record-high values of 250 A/W at 980 nm/20 nW and 990 A/W at 532 nm/60 nW, both at 3.5 V bias. Moreover, due to the embedded quantum discs, the photoresponse covers a broad spectral range from about 0.70 to 2.5 eV, in effect outperforming conventional single InGaAs detectors and dual Si/Ge detectors. The high responsivity, and related gain, results from a novel proposed photogating mechanism, induced by the complex charge carrier dynamics involving optical excitation and recombination in the quantum discs and interface traps, which reduces the electron transport barrier between the highly doped n+ contact and the i-segment. The experimental results obtained are in perfect agreement with the proposed theoretical model and represent a significant step forward toward understanding gain in nanoscale photodetectors and realization of commercially viable broadband photon detectors with ultrahigh gain.

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.

Nanowires offer remarkable opportunities for realizing new optoelectronic devices because of their unique fundamental properties. The ability to engineer nanowire heterostructures with large bandgap variations is particularly interesting for technologically important broadband photodetector applications. Here we report on infrared photodetectors based on arrays of InP nanowires with embedded InAsP quantum discs. We demonstrate a strongly reduced dark current in the detector elements by compensating the unintentional n-doping in the nominal intrinsic region of the InP nanowires by in-situ doping with Zn, a crucial step towards realizing high-performance devices. The optimized array detectors show a broad spectral sensitivity at normal incidence for wavelengths from visible to far-infrared up to 20 μm, promoted by both interband and intersubband transitions. Optical simulations show that the unexpected normal incidence response at long wavelengths is due to non-zero longitudinal modes hosted by the nanowires.

We present an optical design study on a nanowire heterojunction bipolar transistor solar cell. The simple structure of this novel architecture of double-junction solar cell, allows for independent power extraction from the two junctions and makes the nanowire growth easier than in current-matched double-junction solar cells as there is no need for tunnel junctions and only three main semiconductor regions must be grown. We show that the nanowire heterojunction bipolar transistor solar cell design results in an optical performance similar to comparable planar devices, with the nanowires only covering 1/3 of the substrate area. Furthermore, it allows for the growth of lattice-mismatched semiconductor combinations, which increases the detailed balance efficiency limit.

Neural node components consisting of III-V nanowire devices are introduced. This allows for the construction of a small footprint specialized neural network. A broadcasting strategy is developed which removes the need for inter-node wiring. As a model system, an insect brain navigational circuit is chosen and successfully emulated using the introduced nodes and network architecture. The results are based on electronic transport simulations in each device as well as finite-difference time-domain simulations for the broadcasting of optical signals.

We report on a solar cell using bottom-up synthesized InP nanowire arrays with an independently verified power conversion efficiency of 16.7% under AM1.5G solar spectrum. This value, which is the highest reported efficiency for bottom-up synthesized nanowire solar cells, was reached after a stabilized improvement of the device during characterization, by improving both back and front contacts of the more than five million nanowires that are connected in parallel in our solar cell.

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.]

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.

Core-shell nanowires offer great potential to enhance the efficiency of light-emitting diodes (LEDs) and expand the attainable wavelength range of LEDs over the whole visible spectrum. Additionally, nanowire (NW) LEDs can offer both improved light extraction and emission enhancement if the diameter of the wires is not larger than half the emission wavelength (λ/2). However, AlGaInP nanowire LEDs have so far failed to match the high efficiencies of traditional planar technologies, and the parameters limiting the efficiency remain unidentified. In this work, we show by experimental and theoretical studies that the small nanowire dimensions required for efficient light extraction and emission enhancement facilitate significant loss currents, which result in a low efficiency in radial NW LEDs in particular. To this end, we fabricate AlGaInP core-shell nanowire LEDs where the nanowire diameter is roughly equal to λ/2, and we find that both a large loss current and a large contact resistance are present in the samples. To investigate the significant loss current observed in the experiments in more detail, we carry out device simulations accounting for the full 3D nanowire geometry. According to the simulations, the low efficiency of radial AlGaInP nanowire LEDs can be explained by a substantial hole leakage to the outer barrier layer due to the small layer thicknesses and the close proximity of the shell contact. Using further simulations, we propose modifications to the epitaxial structure to eliminate such leakage currents and to increase the efficiency to near unity without sacrificing the λ/2 upper limit of the nanowire diameter. To gain a better insight of the device physics, we introduce an optical output measurement technique to estimate an ideality factor that is only dependent on the quasi-Fermi level separation in the LED. The results show ideality factors in the range of 1-2 around the maximum LED efficiency even in the presence of a very large voltage loss, indicating that the technique is especially attractive for measuring nanowire LEDs at an early stage of development before electrical contacts have been optimized. The presented results and characterization techniques form a basis of how to simultaneously optimize the electrical and optical efficiency of core-shell nanowire LEDs, paving the way to nanowire light emitters that make true use of larger-than-unity Purcell factors and the consequently enhanced spontaneous emission.

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 demonstrate a novel and rapid method for nanowire (NW) solar cell processing. NW arrays were embedded in photoresist. The strong absorption of light in the NWs leads to self-limited exposure of the resist, which enables selective removal of the exposed part of the resist, opening up for the tips of the NWs and further processing. The UV-exposure technology allows a fast and low-cost process compared to the conventional reactive ion etching method.

Electron beam induced current (EBIC) is a well-established tool to, among others, locate and analyze p-n junctions, Schottky contacts or heterostructures in planar devices and is now becoming essential to study and optimize devices at the nanoscale, like III-V nanowire (NW) based solar cells. Here, we report on EBIC measurements on III-V single NW solar cells as well as on fully processed NW devices. This paper also highlights the importance of EBIC to optimize short circuit current density values of fully processed nanowire solar cells of 1 mm2.

The opportunity to engineer III-V nanowires in wurtzite and zinc blende crystal structure allows for exploring properties not conventionally available in the bulk form as well as opening the opportunity for use of additional degrees of freedom in device fabrication. However, the fundamental understanding of the nature of polytypism in III-V nanowire growth is still lacking key ingredients to be able to connect the results of modeling and experiments. Here we show InP nanowires of both pure wurtzite and pure zinc blende grown simultaneously on the same InP [100]-oriented substrate. We find wurtzite nanowires to grow along [Formula: see text] and zinc blende counterparts along [Formula: see text]. Further, we discuss the nucleation, growth, and polytypism of our nanowires against the background of existing theory. Our results demonstrate, first, that the crystal growth conditions for wurtzite and zinc blende nanowire growth are not mutually exclusive and, second, that the interface energies predominantly determine the crystal structure of the nanowires.

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

The surface area of a building that could potentially be used for Building Integrated Photovoltaics would increase dramatically with the availability of transparent solar cells that could replace windows. The challenge is to capture energy from outside the visible region (UV or IR) while simultaneously allowing a high-quality observation of the outside world and transmitting sufficient light in the visible region to satisfactorily illuminate the interior of the building. In this paper, we show both computationally and experimentally that InP nanowire arrays can have good transparency in the visible region and high absorption in the near-infrared region. We show experimentally that we can achieve mean transparencies in the visible region of 65% and the radiative limit of more than 10% based on measured absorption and calculated emission. Our results demonstrate that nanowire arrays hold promise as a method to achieve transparent solar cells, which would fulfill the requirements to function as windows. In addition, we show that by optical design and by designing the geometry of nanowire arrays, solar cells can be achieved that absorb/transmit at wavelengths that are not decided by the bandgap of the material and that can be tailored to specific requirements such as colorful windows.

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.

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.

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 vertical nanowire arrays have great potential for next generation photovoltaics. Development towards high performing nanowire solar cells, which consist of a parallel connection of millions of single nanowire solar cells, requires a fast characterization technique that establishes a link between device performance and device processing. In this work, we use electron beam induced current measurements to characterize fully processed InP nanowire array solar cells at the nanoscale. Non-functional areas on fully processed devices can be quickly identified and processing induced effects on device performance can be clearly distinguished from those arising from nanowire growth. We identify how limiting factors on device performance are related to the processing procedures and provide a path to improve device performance further. In this way, electron beam induced current measurements become an essential tool for nanowire solar cell efficiency optimization, providing fast and useful information at the nanoscale and thus enabling up-scaling of the technology.

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.

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.

Measuring lifetime of photogenerated charges in semiconductor nanowires (NW) is important for understanding light-induced processes in these materials and is relevant for their photovoltaic and photodetector applications. In this paper, we investigate the dynamics of photogenerated charge carriers in a series of as-grown InP NW with different levels of sulfur (S) doping. We observe that photoluminescence (PL) decay time as well as integrated PL intensity decreases with increasing S doping. We attribute these observations to hole trapping with the trap density increased due to S-doping level followed by nonradiative recombination of trapped charges. This assignment is proven by observation of the trap saturation in three independent experiments: via excitation power and repetition rate PL lifetime dependencies and by PL pump-probe experiment.

Optical reflectometry is commonly used as an accurate and noninvasive characterization tool when growing planar semiconductor layers. However, thin-film analysis schemes cannot be directly applied to nanowire systems due to their complex optical response. Here, we report on reliable in situ characterization of nanowire growth with high accuracy using optical reflectance spectra for analysis. The method makes it possible to determine the nano-wire length, diameter, and growth rate in situ in real time with high resolution. We demonstrate the method's versatility by using the optical reflectance data for determining nanowire dimensions on both particle-assisted and selective-area grown nanowires. To indicate the full potential of in situ characterization of nanowire synthesis we evaluate the growth dynamics of InP nanowires in the presence of the p-type dopant precursor diethylzinc. We observe that the growth rate is strongly affected by the diethylzinc. At low diethylzinc flows, the growth rate decreases monotonously while higher flows lead to an initially increasing growth rate. From these in situ characterization data, we conclude that the surface migration length of adatom species is affected strongly by the addition of diethylzinc. We believe that this characterization method will become a standard tool for in situ growth monitoring and aid in elucidating the complex growth dynamics often exhibited during nanowire growth. (Less)

We have compared the absorption in InP core-shell nanowire p-i-n junctions in lateral and vertical orientation. Arrays of vertical core-shell nanowires with 400 nm pitch and 280 nm diameter, as well as corresponding lateral single core-shell nanowires, were configured as photovoltaic devices. The photovoltaic characteristics of the samples, measured under 1 sun illumination, showed a higher absorption in lateral single nanowires compared to that in individual vertical nanowires, arranged in arrays with 400 nm pitch. Electromagnetic modeling of the structures confirmed the experimental observations and showed that the absorption in a vertical nanowire in an array depends strongly on the array pitch. The modeling demonstrated that, depending on the array pitch, absorption in a vertical nanowire can be lower or higher than that in a lateral nanowire with equal absorption predicted at a pitch of 510 nm for our nanowire geometry. The technology described in this Letter facilitates quantitative comparison of absorption in laterally and vertically oriented core-shell nanowire p-i-n junctions and can aid in the design, optimization, and performance evaluation of nanowire-based core-shell photovoltaic devices.

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.

Nanowire solar cells with single p-n junction have had a rapid increase in energy conversion efficiency. Introducing tandem geometry is the path for higher efficiency, for which nanowire tunnel diode is a critical component. We fabricated, and characterized the GalnP flnP nanowire tunnel diodes with bandgap combinations suitable for a tandem junction solar cell. The electrical contact was improved by using different n type dopant species for the heterojunction and the nanowire contacting area, respectively. A GalnP/lnP nanowire tunnel diode with an average measured peak current density of 45 A/cm2and maximum peak to valley ratio of 2.4 was demonstrated. The demonstration of GalnP/lnP tunnel diodes lays the foundation for the next step of realizing NW tandem j unction solar cells.

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

Semiconductor nanowires are a class of materials recently gaining increasing interest for solar cell applications. In this article we review the development of the field with a special focus on the III–V materials due to their potential to reach high power conversion efficiencies. After introducing basic concepts of nanowire synthesis, we discuss important aspects of nanowire design for high power conversion efficiencies; first in terms of light absorption, then in terms of charge carrier separation and collection. Further, we examine methods to assess and understand the materials quality and the solar cell performance. We end the review by a discussion of strategies and challenges in achieving efficiencies above the Shockley-Queisser limit, and the potential for cost efficient production.

An understanding of the absorption of light is essential for efficient photovoltaic and photodetection applications with III–V nanowire arrays. Here, we correlate experiments with modeling and verify experimentally the predicted absorption of light in InP nanowire arrays for varying nanowire diameter and length. We find that 2,000 nm long nanowires in a pitch of 400 nm can absorb 94% of the incident light with energy above the band gap and, as a consequence, light which in a simple ray-optics description would be travelling between the nanowires can be efficiently absorbed by the nanowires. Our measurements demonstrate that the absorption for long nanowires is limited by insertion reflection losses when light is coupled from the air top-region into the array. These reflection losses can be reduced by introducing a smaller diameter to the nanowire-part closest to the air top-region. For nanowire arrays with such a nanowire morphology modulation, we find that the absorptance increases monotonously with increasing diameter of the rest of the nanowire.

We report on electrical and optical properties of p+-i-n+ photodetectors/solar cells based on square millimeter arrays of InP nanowires (NWs) grown on InP substrates. The study includes a sample series where the p+-segment length was varied between 0 and 250 nm, as well as solar cells with 9.3% efficiency with similar design. The electrical data for all devices display clear rectifying behavior with an ideality factor between 1.8 and 2.5 at 300 K. From spectrally resolved photocurrent measurements, we conclude that the photocurrent generation process depends strongly on the p+-segment length. Without a p+-segment, photogenerated carriers funneled from the substrate into the NWs contribute strongly to the photocurrent. Adding a p+-segment decouples the substrate and shifts the depletion region, and collection of photogenerated carriers, to the NWs, in agreement with theoretical modeling. In optimized solar cells, clear spectral signatures of interband transitions in the zinc blende and wurtzite InP layers of the mixed-phase i-segments are observed. Complementary electroluminescence, transmission electron microscopy (TEM), as well as measurements of the dependence of the photocurrent on angle of incidence and polarization, support our interpretations.

In this work, growth of InN quantum dots (QDs) on GaN nanowires (NWs) by metal-organic vapour phase epitaxy is demonstrated, illustrating the feasibility to combine 0D and 1D structures for nitride semiconductors. Selective area growth was used to generate arrays of c-oriented GaN NWs using Si3N4 as the mask material. In general, InN QDs tend to form at the NW edges between the m-plane side facets, but the QD growth can also be tuned to the side facets by controlling the growth temperature and the growth rate. TEM characterization reveals that I1-type stacking faults are formed in the QDs and originate from the misfit dislocations at the InN/GaN interface. Photoluminescence measurement at 4 K shows that the peak shifts to high energy with reduced dot size. (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)