Semiconductor Nanowire Arrays Research Articles

Heterostructured semiconductor nanowire arrays for artificial photosynthesis

A critical summary and insight into recent advances in artificial photosynthesis over heterostructured semiconductor nanowire arrays have been presented, which concisely describe the current status and possible future research directions in this promising research area.

Nanowire dopant measurement using secondary ion mass spectrometry

A method is presented to improve the quantitative determination of dopant concentration in semiconductor nanowire (NW) arrays using secondary ion mass spectrometry (SIMS). SIMS measurements were used to determine Be dopant concentrations in a Be-doped GaAs thin film and NW arrays of various pitches that were dry-etched from the same film. A comparison of these measurements revealed a factor of 3 to 12 difference, depending on the NW array pitch, between the secondary Be ion yields of the film and the NW arrays, despite being identically doped. This was due to matrix effects and ion beam mixing of Be from the NWs into the surrounding benzocyclobutene that was used to fill the space between the NWs. This indicates the need for etched NWs to be used as doping standards instead of 2D films when evaluating NWs of unknown doping by SIMS. Using the etched NWs as doping standards, NW arrays of various pitches grown by the vapour-liquid-solid mechanism were characterized by SIMS to yield valuable insights into doping mechanisms.

Using Activated Transport in Parallel Nanowires for Energy Harvesting and Hot-Spot Cooling

We study arrays of parallel doped semiconductor nanowires in a temperature range where the electrons propagate through the nanowires by phonon assisted hops between localized states. By solving the Random Resistor Network problem, we compute the thermopower $S$, the electrical conductance $G$, and the electronic thermal conductance $K^e$ of the device. We investigate how those quantities depend on the position -- which can be tuned with a back gate -- of the nanowire impurity band with respect to the equilibrium electrochemical potential. We show that large power factors can be reached near the band edges, when $S$ self-averages to large values while $G$ is small but scales with the number of wires. Calculating the amount of heat exchanged locally between the electrons inside the nanowires and the phonons of the environment, we show that phonons are mainly absorbed near one electrode and emitted near the other when a charge current is driven through the nanowires near their band edges. This phenomenon could be exploited for a field control of the heat exchange between the phonons and the electrons at submicron scales in electronic circuits. It could be also used for cooling hot spots.

Shockley–Queisser Detailed Balance Efficiency Limit for Nanowire Solar Cells

III–V semiconductor nanowire arrays show promise as a platform for next-generation solar cells. However, the theoretical efficiency limit for converting the energy of sunlight into electrical energy in such solar cells is unknown. Here, we calculate through electromagnetic modeling the Shockley–Queisser efficiency limit for an InP nanowire array solar cell. In this analysis, we calculate first from the absorption of sunlight the short-circuit current. Next, we calculate the voltage-dependent emission characteristics of the nanowire array. From these processes, we identify how much current we can extract at a given voltage. Finally, after constructing this current–voltage (IV) curve of the nanowire solar cell, we identify from the maximum power output the maximum efficiency. We compare this efficiency of the nanowire array with the 31.0% efficiency limit of the conventional InP bulk solar cell with an inactive substrate underneath. We consider a nanowire array of 400 nm in period, which shows a high short-circuit current. We optimize both the nanowire length and diameter in our analysis. For example, nanowires of 4 μm in length and 170 nm in diameter produce 96% of the short-circuit current obtainable in the perfectly absorbing InP bulk cell. However, the nanowire solar cell emits fewer photons than the bulk cell at thermal equilibrium, especially into the substrate. This weaker emission allows for a higher open circuit-voltage for the nanowire cell. As an end result, nanowires longer than 4 μm can actually show, despite producing a lower short-circuit current, a higher efficiency limit, of up to 32.5%, than the bulk cell.

Maximizing the ultimate absorption efficiency of vertically-aligned semiconductor nanowire arrays with wires of a low absorption cross-section

Single semiconducting nanowires with sub-wavelength diameters exhibit superior light absorption, and hence triggered a vivid discussion regarding the application of these nanostructures into future generations of high efficiency solar cells. We examine the transition from a single highly absorbing silicon wire into an array composed of such individuals in order to validate the application of these into solar harvesting devices. We use finite-difference time-domain simulations to show that the coupling of the Fabry–Perot oscillations with the waveguide resonances inside the wires has a significant effect on the array absorption. For example, the ultimate absorption efficiency of a square-tiled wire array under normal incidence (array period of 0.5µm, wire diameter of 0.4µm and wire height of 2) is 81% higher than a 2µm thin-film when the Fabry–Perot oscillations are considered and 37% higher when these oscillations are not considered. This coupling screens out the contribution of the waveguide modes to the array absorption and therefore, unlike previously published work, we eliminate the contribution of the Fabry–Perot oscillations. In this manner we demonstrate the absorption enhancement due to waveguide modes, and general correlations between the nanowire geometry and the overall array absorption are presented. First, we show that once an isolated wire with high absorption cross-section is nested inside an array its absorption decreases due to wire proximity effects. Secondly, the array absorption is maximized with relatively wide wires of low absorption cross-sections. We show that a 75nm wire inside an square-tiled array with 2µm period has an average absorption efficiency factor of 6.5 and the average relative absorption of the array is 0.5%, while the same wire nested inside an array of a 0.25µm period exhibits 2.3 average absorption efficiency factor and the array exhibits average relative absorption of 9.85%. Finally, there is an optimized wire diameter that once exceeded the array absorption converges to that of a continuous film. For example, the maximum absorption of 0.5µm array is obtained with wire diameter of 0.4µm where a decrease in relative absorption is recorded for arrays with wires exceeding 0.4µm.

Application of free-standing InP nanowire arrays and their optical properties for resource-saving solar cells

III–V compound semiconductor nanowire (NW) arrays have exhibited remarkable behavior in photovoltaic applications. We embedded an orderly vertical InP NW array in poly(dimethylsiloxane) (PDMS) and peeled it off from the substrate to form a AuZn contact. The sample with the substrate exhibited a very high average absorptance of 92%. However, when the array was peeled off, the optical absorptance degraded, particularly in the longer-wavelength region. After the AuZn was deposited on the back side of the NW array, the absorptance increased. This technology could enable a new approach for NW-based photovoltaics with a lower fabrication cost.

Resonant absorption in semiconductor nanowires and nanowire arrays: Relating leaky waveguide modes to Bloch photonic crystal modes

We present a unified framework for resonant absorption in periodic arrays of high index semiconductor nanowires that combines a leaky waveguide theory perspective and that of photonic crystals supporting Bloch modes, as array density transitions from sparse to dense. Full dispersion relations are calculated for each mode at varying illumination angles using the eigenvalue equation for leaky waveguide modes of an infinite dielectric cylinder. The dispersion relations along with symmetry arguments explain the selectivity of mode excitation and spectral red-shifting of absorption for illumination parallel to the nanowire axis in comparison to perpendicular illumination. Analysis of photonic crystal band dispersion for varying array density illustrates that the modes responsible for resonant nanowire absorption emerge from the leaky waveguide modes.

Space-and-time current spectroscopy of nanostructured selenium in the chrysotile asbestos matrix

The non-steady-state photoelectromotive force effect was experimentally studied in a semiconductor nanowire array, i.e., in a composite representing selenium in a chrysotile asbestos matrix. The sample was exposed to an oscillating interference pattern, and the material response was measured as an alternating electric current. The experiments were performed for two geometries in which the excited photocurrent was parallel or perpendicular to nanowires. The dependences of the signal amplitude on the phase modulation frequency, spatial frequency, light polarization, and temperature were obtained. The photoelectric parameters of the material were determined for the light wavelength λ = 633 nm. The effect was theoretically analyzed for the semiconductor model with shallow traps, which allowed the explanation of the observed increase in the signal amplitude in the presence of additional phase modulation.

Photoelectrochemical hydrogen production on InP nanowire arrays with molybdenum sulfide electrocatalysts.

Semiconductor nanowire arrays are expected to be advantageous for photoelectrochemical energy conversion due to their reduced materials consumption. In addition, with the nanowire geometry the length scales for light absorption and carrier separation are decoupled, which should suppress bulk recombination. Here, we use vertically aligned p-type InP nanowire arrays, coated with noble-metal-free MoS3 nanoparticles, as the cathode for photoelectrochemical hydrogen production from water. We demonstrate a photocathode efficiency of 6.4% under Air Mass 1.5G illumination with only 3% of the surface area covered by nanowires.

Nanowire antenna absorption probed with time-reversed fourier microscopy.

Understanding light absorption in individual nanostructures is crucial for optimizing the light-matter interaction at the nanoscale. Here, we introduce a technique named time-reversed Fourier microscopy that enables the measurement of the angle-dependent light absorption in dilute arrays of uncoupled semiconductor nanowires. Because of their large separation, the nanowires have a response that can be described in terms of individual nanostructures. The geometry of individual nanowires makes them behave as nanoantennas that show a strong interaction with the incident light. The angle-dependent absorption measurements, which are compared to numerical simulations and Mie scattering calculations, show the transition from guided-mode to Mie-resonance absorption in individual nanowires and the relative efficiency of these two absorption mechanisms in the same nanostructures. Mie theory fails to describe the absorption in finite-length vertical nanowires illuminated at small angles with respect to their axis. At these angles, the incident light is efficiently absorbed after being coupled to guided modes. Our findings are relevant for the design of nanowire-based photodetectors and solar cells with an optimum efficiency.

Semiconductor nanowire solar cells: synthetic advances and tunable properties

Abstract The solar power received by Earth far exceeds global power demands. Despite this, infrastructure shortages and high capital costs prevent the wide-scale adoption of photovoltaics to displace conventional energy technologies relying on carbon-based fuels. In response, new concepts and materials have been explored to develop next-generation solar cells capable of operating more efficiently and cheaply. Over the past decade, single semiconductor nanowire (NW) and NW array devices have emerged as promising platforms with which to examine new concepts. Small distances in NWs allow for efficient charge separation while tunable photonic modes permit light absorption properties distinct from bulk materials. Furthermore, the synthesis and fabrication of NW devices presents new opportunities such as with incorporation of complex heterostructures or use of cheaper substrates. Here, we present a critical discussion of the benefits and remaining challenges related to utilization of NWs for solar energy conversion and emphasize the synthetic advances leading towards significant improvement in the electrical and optical performance of NW devices. We conclude by articulating the unique capabilities of solar cells assembled from multiple, distinct NWs.

Molecular Motor Propelled Filaments Reveal Light-Guiding in Nanowire Arrays for Enhanced Biosensing

Semiconductor nanowire arrays offer significant potential for biosensing applications with optical read-out due to their high surface area and due to the unique optical properties of one-dimensional materials. A challenge for optical read-out of analyte-binding to the nanowires is the need to efficiently collect and detect light from a three-dimensional volume. Here we show that light from fluorophores attached along several μm long vertical Al2O3 coated gallium phosphide nanowires couples into the wires, is guided along them and emitted at the tip. This enables effective collection of light emitted by fluorescent analytes located at different focal planes along the nanowire. We unequivocally demonstrate the light-guiding effect using a novel method whereby the changes in emitted fluorescence intensity are observed when fluorescent cytoskeletal filaments are propelled by molecular motors along the wires. The findings are discussed in relation to nanobiosensor developments, other nanotechnological applications, and fundamental studies of motor function.

Optical Simulation of Multijunction Solar Cells Based on III-V Nanowires on Silicon

Arrays of III-V direct-bandgap semiconductor nanowires are promising candidates for future photovoltaic devices due to their high optical absorption and their ability to be grown on low cost semiconductor substrates like silicon. The core-shell structure is particularly interesting as the electron-hole pair separation occurs in the radial direction and the photogenerated minority carriers have to travel short distances (the radius of the nanowires) thus improving the collection probability in case of well passivated nanowire surfaces.The aim of this study is to find the optimal geometry (length, height and diameter) of a GaAs nanowire array grown on a silicon substrate in order to have the best absorption of the incident photons. For this purpose, we have performed electromagnetic simulations with a homemade Rigorous Coupled Wave Analysis (RCWA) software. Our simulations take into account the core-shell structure, the passivation layer (GaAlAs) and the anti-reflection coating, but also the necessity to achieve current matching between the GaAs nanowire-based and the silicon substrate solar cells. This requirement is justified by the fact that the final goal is to process a tandem solar cell with junctions connected in series.

III–V nanowire arrays: growth and light interaction

Semiconductor nanowire arrays are reproducible and rational platforms for the realization of high performing designs of light emitting diodes and photovoltaic devices. In this paper we present an overview of the growth challenges of III–V nanowire arrays obtained by molecular beam epitaxy and the design of III–V nanowire arrays on silicon for solar cells. While InAs tends to grow in a relatively straightforward manner on patterned (111)Si substrates, GaAs nanowires remain more challenging; success depends on the cleaning steps, annealing procedure, pattern design and mask thickness. Nanowire arrays might also be used for next generation solar cells. We discuss the photonic effects derived from the vertical configuration of nanowires standing on a substrate and how these are beneficial for photovoltaics. Finally, due to the special interaction of light with standing nanowires we also show that the Raman scattering properties of standing nanowires are modified. This result is important for fundamental studies on the structural and functional properties of nanowires.

Ultrahigh Density Array of Vertically Aligned Small-molecular Organic Nanowires on Arbitrary Substrates

In recent years π-conjugated organic semiconductors have emerged as the active material in a number of diverse applications including large-area, low-cost displays, photovoltaics, printable and flexible electronics and organic spin valves. Organics allow (a) low-cost, low-temperature processing and (b) molecular-level design of electronic, optical and spin transport characteristics. Such features are not readily available for mainstream inorganic semiconductors, which have enabled organics to carve a niche in the silicon-dominated electronics market. The first generation of organic-based devices has focused on thin film geometries, grown by physical vapor deposition or solution processing. However, it has been realized that organic nanostructures can be used to enhance performance of above-mentioned applications and significant effort has been invested in exploring methods for organic nanostructure fabrication. A particularly interesting class of organic nanostructures is the one in which vertically oriented organic nanowires, nanorods or nanotubes are organized in a well-regimented, high-density array. Such structures are highly versatile and are ideal morphological architectures for various applications such as chemical sensors, split-dipole nanoantennas, photovoltaic devices with radially heterostructured "core-shell" nanowires, and memory devices with a cross-point geometry. Such architecture is generally realized by a template-directed approach. In the past this method has been used to grow metal and inorganic semiconductor nanowire arrays. More recently π-conjugated polymer nanowires have been grown within nanoporous templates. However, these approaches have had limited success in growing nanowires of technologically important π-conjugated small molecular weight organics, such as tris-8-hydroxyquinoline aluminum (Alq3), rubrene and methanofullerenes, which are commonly used in diverse areas including organic displays, photovoltaics, thin film transistors and spintronics. Recently we have been able to address the above-mentioned issue by employing a novel "centrifugation-assisted" approach. This method therefore broadens the spectrum of organic materials that can be patterned in a vertically ordered nanowire array. Due to the technological importance of Alq3, rubrene and methanofullerenes, our method can be used to explore how the nanostructuring of these materials affects the performance of aforementioned organic devices. The purpose of this article is to describe the technical details of the above-mentioned protocol, demonstrate how this process can be extended to grow small-molecular organic nanowires on arbitrary substrates and finally, to discuss the critical steps, limitations, possible modifications, trouble-shooting and future applications.

Efficient light management in vertical nanowire arrays for photovoltaics

Vertical arrays of direct band gap III-V semiconductor nanowires (NWs) hold the prospect of cheap and efficient next-generation photovoltaics, and guidelines for successful light-management are needed. Here, we use InP NWs as a model system and find, through electrodynamic modeling, general design principles for efficient absorption of sun light in nanowire arrays by systematically varying the nanowire diameter, the nanowire length, and the array period. Most importantly, we discover the existence of specific band-gap dependent diameters, 170 nm and 410 nm for InP, for which the absorption of sun light in the array is optimal, irrespective of the nanowire length. At these diameters, the individual InP NWs of the array absorb light strongly for photon energies just above the band gap energy due to a diameter-tunable nanophotonic resonance, which shows up also for other semiconductor materials of the NWs. Furthermore, we find that for maximized absorption of sun light, the optimal period of the array increases with nanowire length, since this decreases the insertion reflection losses.

Reflection measurements to reveal the absorption in nanowire arrays

The absorption of light is at the core of photovoltaic applications. For many nanostructure-based devices, an assessment of the absorption in the nanostructures is complicated by a thick, opaque substrate that prohibits transmission measurements. Here, we show how a single reflection measurement can be used for approximating the amount of light absorbed in vertical semiconductor nanowire arrays.

Geometrical optics, electrostatics, and nanophotonic resonances in absorbing nanowire arrays

Semiconductor nanowire arrays have shown promise for next-generation photovoltaics and photodetection, but enhanced understanding of the light-nanowire interaction is still needed. Here, we study theoretically the absorption of light in an array of vertical InP nanowires by moving continuously, first from the electrostatic limit to the nanophotonic regime and then to the geometrical optics limit. We show how the absorption per volume of semiconductor material in the array can be varied by a factor of 200, ranging from 10 times weaker to 20 times stronger than in a bulk semiconductor sample.

Radiative recombination mechanisms in individual wurtzite ZnSe nanowires with a defect-free single-crystalline microstructure

Photoluminescence (PL) spectroscopy performed on arrays of semiconductor nanowires (NWs) suffers from ensemble broadening of PL lines, and fails to separate the PL from NWs of different crystal structures in the ensemble. Even the results on PL from single NWs are not devoid of ambiguity. This is because the influence of structural defects in NWs, such as stacking faults, twin boundaries and dislocations, on their optical spectra cannot be accounted for since the structural characteristics of the same NW remain largely unknown. We performed low-temperature PL spectroscopy on individual wurtzite (WZ) ZnSe NWs, and confirmed a homogeneous single-crystalline microstructure without any extended defects in these NWs, thus excluding any role of structural imperfections in their optical spectra. The luminescence is shown to be dominated solely by native point defects, while no role of extrinsic impurities was found. The radiative recombination is shown to originate from excitons bound to vacancies of Zn (VZn), VZn-complexes, and their phonon replicas. The binding energies of the acceptor-bound excitons, ionization energies of the acceptors, and average number of phonons emitted for shallow donor-VZn acceptor pair related transition were determined. Distinct from previous studies on PL from arrays of ZnSe NWs, this work provides an unambiguous interpretation of the PL spectra and assignment of PL peaks to WZ ZnSe. Narrow excitonic emission of linewidths 2.9 meV indicate excellent optical quality of WZ ZnSe NWs.

Semiconductor nanowires: a platform for exploring limits and concepts for nano-enabled solar cells

Over the past decade extensive studies of single semiconductor nanowire and nanowire array photovoltaic devices have explored the potential of these materials as platforms for a new generation of efficient and cost-effective solar cells. This feature review discusses strategies for implementation of semiconductor nanowires in solar energy applications, including advances in complex nanowire synthesis and characterization, fundamental insights from characterization of devices, utilization and control of the unique optical properties of nanowires, and new strategies for assembly and scaling of nanowires into diverse arrays that serve as a new paradigm for advanced solar cells.