Nanowire Ensembles Research Articles

Optoelectronic properties of p-diamond/n-GaN nanowire heterojunctions

In this work, nanodiodes comprised of n-GaN nanowires on p-diamond substrates are investigated. The electric transport properties are discussed on the basis of simulations and determined experimentally for individual p-diamond/n-GaN nanodiodes by applying conductive atomic force microscopy. For low doping concentrations, a high rectification ratio is observed. The fabrication of a prototype nanoLED device on the basis of ensemble nanowire contacts is presented, showing simultaneous electroluminescence in the UV and the green spectral range which can be ascribed to hole injection into the n-GaN nanowires and electron injection into the p-diamond, respectively. In addition, the operation and heat distribution of the nanoLED device are visualized by active thermographic imaging.

Improved control over spontaneously formed GaN nanowires in molecular beam epitaxy using a two-step growth process

We investigate the influence of modified growth conditions during the spontaneous formation of GaN nanowires (NWs) on Si(111) in plasma-assisted molecular beam epitaxy. We find that a two-step growth approach, where the substrate temperature is increased during the nucleation stage, is an efficient method to gain control over the area coverage, average diameter, and coalescence degree of GaN NW ensembles. Furthermore, we also demonstrate that the growth conditions employed during the incubation time that precedes nanowire nucleation do not influence the properties of the final nanowire ensemble. Therefore, when growing GaN NWs at elevated temperatures or with low Ga/N ratios, the total growth time can be reduced significantly by using more favorable growth conditions for nanowire nucleation during the incubation time.

Bandgap tuning of GaAs/GaAsSb core-shell nanowires grown by molecular beam epitaxy

Semiconductor nanowires have been identified as a viable technology for next-generation infrared (IR) photodetectors with improved detectivity and detection across a range of energies as well as for novel single-photon detection in quantum networking. The GaAsSb materials system is especially promising in the 1.3–1.55 μm spectral range. In this work we present band-gap tuning up to 1.3 μm in GaAs/GaAsSb core–shell nanowires, by varying the Sb content using Ga-assisted molecular beam epitaxy. An increase in Sb content leads to strain accumulation in shell manifesting in rough surface morphology, multifaceted growths, curved nanowires, and deterioration in the microstructural and optical quality of the nanowires. The presence of multiple PL peaks for Sb compositions ≥12 at.% and degradation in the nanowire quality as attested by broadening of Raman and x-ray diffraction peaks reveal compositional instability in the nanowires. Transmission electron microscope (TEM) images show the presence of stacking faults and twins. Based on photoluminescence (PL) peak energies and their excitation power dependence behavior, an energy-band diagram for GaAs/GaAsSb core–shell nanowires is proposed. Optical transitions are dominated by type II transitions at lower Sb compositions and a combination of type I and type II transitions for compositions ≥12 at.%. Type I optical transitions as low as 0.93 eV (1.3 μm) from the GaAsSb for Sb composition of 26 at.% have been observed. The PL spectrum of a single nanowire is replicated in the ensemble nanowires, demonstrating good compositional homogeneity of the latter. A double-shell configuration for passivation of deleterious surface states leads to significant enhancement in the PL intensity resulting in the observation of room temperature emission, which provides significant potential for further improvement with important implications for nanostructured optoelectronic devices operating in the near-infrared regime.

Nonpolar p-GaN/n-Si heterojunction diode characteristics: a comparison between ensemble and single nanowire devices

The electrical and photodiode characteristics of ensemble and single p-GaN nanowire and n-Si heterojunction devices were studied. Ideality factor of the single nanowire p-GaN/n-Si device was found to be about three times lower compared to that of the ensemble nanowire device. Apart from the deep-level traps in p-GaN nanowires, defect states due to inhomogeneity in Mg dopants in the ensemble nanowire device are attributed to the origin of the high ideality factor. Photovoltaic mode of the ensemble nanowire device showed an improvement in the fill-factors up to 60% over the single nanowire device with fill-factors up to 30%. Responsivity of the single nanowire device in the photoconducting mode was found to be enhanced by five orders, at 470 nm. The enhanced photoresponse of the single nanowire device also confirms the photoconduction due to defect states in p-GaN nanowires.

Localized Charge Transfer Process and Surface Band Bending in Methane Sensing by GaN Nanowires

The physicochemical processes at the surfaces of semiconductor nanostructures involved in electrochemical and sensing devices are strongly influenced by the presence of intrinsic or extrinsic defects. To reveal the surface controlled sensing mechanism, intentional lattice oxygen defects are created on the surfaces of GaN nanowires for the elucidation of charge transfer process in methane (CH4) sensing. Experimental and simulation results of electron energy loss spectroscopy (EELS) studies on oxygen rich GaN nanowires confirmed the possible presence of 2(ON) and VGa-3ON defect complexes. A global resistive response for sensor devices of ensemble nanowires and a localized charge transfer process in single GaN nanowires are studied in situ scanning by Kelvin probe microscopy (SKPM). A localized charge transfer process, involving the VGa-3ON defect complex on nanowire surface is attributed in controlling the global gas sensing behavior of the oxygen rich ensemble GaN nanowires.

Self-Equilibration of the Diameter of Ga-Catalyzed GaAs Nanowires.

Designing strategies to reach monodispersity in fabrication of semiconductor nanowire ensembles is essential for numerous applications. When Ga-catalyzed GaAs nanowire arrays are grown by molecular beam epitaxy with help of droplet-engineering, we observe a significant narrowing of the diameter distribution of the final nanowire array with respect to the size distribution of the initial Ga droplets. Considering that the droplet serves as a nonequilibrium reservoir of a group III metal, we develop a model that demonstrates a self-equilibration effect on the droplet size in self-catalyzed III-V nanowires. This effect leads to arrays of nanowires with a high degree of uniformity regardless of the initial conditions, while the stationary diameter can be further finely tuned by varying the spacing of the array pitch on patterned Si substrates.

High-Temperature Growth of GaN Nanowires by Molecular Beam Epitaxy: Toward the Material Quality of Bulk GaN

In molecular beam epitaxy, the spontaneous formation of GaN nanowires on Si(111) substrates at elevated temperatures is limited by the long incubation time that precedes nanowire nucleation. In this work, we present three growth approaches to minimize the incubation time and to thus facilitate significantly higher growth temperatures (up to 875 °C). We achieve this advancement by (i) using III/V flux ratios of >1 to compensate for Ga desorption, (ii) introducing a two-step growth procedure, and (iii) using an AlN buffer layer to favor GaN nucleation. The GaN nanowire ensembles grown at so far unexplored substrate temperatures exhibit excitonic transitions with sub-meV linewidths comparable to those of state-of-the-art free-standing GaN layers grown by hydride vapor phase epitaxy.

Surface gas sensing kinetics of a WO3 nanowire sensor: part 1—oxidizing gases

The gas-sensing mechanism of a one-dimensional nanowire gas sensor was studied based on examination of adsorption–desorption kinetics of oxidizing gases of O2 and NO on a highly porous WO3 nanowire ensemble structure. An identical sensor of a single diameter was used for the examination. The test gases were diluted in either dry air or nitrogen, and reaction temperatures were fixed or varied. We show that the Langmuir adsorption theory applies to the gas surface reactions, and that the detection limit and selectivity of a gas species on a sensor material is determined by the adsorption–desorption reaction kinetics on the surface. Mixed gases, however, interact with each other in the adsorption–desorption processes. The sensor response-and-recovery kinetics is connected to the nanowire conductance in our proposed electron depletion model for nanowire sensors.

Ensembles-of Gold Nanowires for the Anodic Stripping Voltammetric Determination of Inorganic Arsenic.

3D-ensembles of gold nanowires electrodes (3D-NEEs) are produced by electroless gold deposition in track-etched polycarbonate (PC) membranes, followed by partial etching (plama or chemical) of the polymeric membrane. These electrodes are applied to the anodic stripping voltammetric determination of inorganic As. The controlled etching of the PC template increased the gold surface area, widening the linear range of the analytical response with respect to ensembles of gold nanodisk electrodes (2D-NEEs). 3D-NEEs prepared using a chemical etching time of 10 s allows the anodic stripping determination of As(III) with a detection limit of 0.08 μg/L and a linear range extended up to 20 μg/L. The speciation of inorganic As (As(III) and (As(V)) in river water is possible by difference between As(III) and total inorganic As, determined after reduction of As(V) with cysteine. The proposed method is successfully validated by comparison with lCP-MS determination.

In Situ Electrical Conductivity of LixMnO2 Nanowires as a Function of x and Size

Manganese oxide, MnO2, excels as a hybrid electrical energy storage material: The manganese centers in MnO2 are capable of undergoing a reduction from 4+ to 3+ balanced by the intercalation of lithium ions to form LixMnO2 while its conductive surfaces simultaneously store energy as an electrical double layer capacitor. The highest capacitance and power performance for MnO2 has been obtained for ensembles of nanowires that are 200 nm or less in width and many microns in length. Typically such MnO2 nanowires are attached to a current collector at just one end, and electrical conductivity of the nanowire is therefore required in order to maintain a consistent redox and charge state along its axis. The electrical conductance of the nanowire therefore plays a very important role, and yet this parameter has been measured in few previous studies. In this work, we directly measure the electrical conductance of δ-MnO2 nanowires in situ in 1 M LiClO4, acetonitrile as a function of the equilibrium Li content for nan...

Temperature Dependence of Interband Transitions in Wurtzite InP Nanowires.

Semiconductor nanowires (NWs) formed by non-nitride III-V compounds grow preferentially with wurtzite (WZ) lattice. This is contrary to bulk and two-dimensional layers of the same compounds, where only zincblende (ZB) is observed. The absorption spectrum of WZ materials differs largely from their ZB counterparts and shows three transitions, referred to as A, B, and C in order of increasing energy, involving the minimum of the conduction band and different critical points of the valence band. In this work, we determine the temperature dependence (T = 10-310 K) of the energy of transitions A, B, and C in ensembles of WZ InP NWs by photoluminescence (PL) and PL excitation (PLE) spectroscopy. For the whole temperature and energy ranges investigated, the PL and PLE spectra are quantitatively reproduced by a theoretical model taking into account contribution from both exciton and continuum states. WZ InP is found to behave very similarly to wide band gap III-nitrides and II-VI compounds, where the energy of A, B, and C displays the same temperature dependence. This finding unveils a general feature of the thermal properties of WZ materials that holds regardless of the bond polarity and energy gap of the crystal. Furthermore, no differences are observed in the temperature dependence of the fundamental band gap energy in WZ InP NWs and ZB InP (both NWs and bulk). This result points to a negligible role played by the WZ/ZB differences in determining the deformation potentials and the extent of the electron-phonon interaction that is a direct consequence of the similar nearest neighbor arrangement in the two lattices.

Transformation of Ag nanowires into semiconducting AgFeS2 nanowires.

We report on the synthesis of semiconducting AgFeS2 nanowires, obtained from the conversion of Ag nanowires. The study of the conversion process shows that the formation of Ag2S nanowires, as an intermediate step, precedes the conversion into AgFeS2 nanowires. The chemical properties of AgFeS2 nanowires were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy at intermediate steps of the conversion process and show that the temperature at which the reaction takes place is critical to obtaining nanowires as opposed to nanotubes. Optical measurements on nanowire ensembles confirm the semiconducting nature of AgFeS2, with a direct band gap of 0.88 eV.

On the impact of indium distribution on the electronic properties in InGaN nanodisks

We analyze an epitaxially grown heterostructure composed of InGaN nanodisks inserted in GaN nanowires in order to relate indium concentration to the electronic properties. This study was achieved with spatially resolved low-loss electron energy-loss spectroscopy using monochromated electrons to probe optical excitations—plasmons—at nanometer scale. Our findings show that each nanowire has its own indium fluctuation and therefore its own average composition. Due to this indium distribution, a scatter is obtained in plasmon energies, and therefore in the optical dielectric function, of the nanowire ensemble. We suppose that these inhomogeneous electronic properties significantly alter band-to-band transitions and consequently induce emission broadening. In addition, the observation of tailing indium composition into the GaN barrier suggests a graded well-barrier interface leading to further inhomogeneous broadening of the electro-optical properties. An improvement in the indium incorporation during growth is therefore needed to narrow the emission linewidth of the presently studied heterostructures.

Importance of the dielectric contrast for the polarization of excitonic transitions in single GaN nanowires

We investigate the polarization of excitonic transitions of single dispersed GaN nanowires with a diameter of about 50 nm. We observe donor-bound exciton transitions with a linewidth narrower than 250 μeV at 10 K, whereas the luminescence from free excitons exhibits a width of up to 5 meV. This broadening is larger than that observed for free excitons in the as-grown nanowire ensemble and is the result of inhomogeneous strain introduced by the nanowire dispersion. This strain lowers the symmetry of the lattice structure and allows A excitons to emit light polarized parallel to the nanowire axis. The polarization anisotropy of A excitons, however, is found to largely vary from one nanowire to another. In addition, the various bound-exciton lines in a given nanowire do not show the same polarization anisotropies. These findings can be explained by the dielectric contrast between the nanowire and its environment, but only when taking into account the strong variations of the dielectric function of GaN at the near band-edge.

Monitoring the formation of nanowires by line-of-sight quadrupole mass spectrometry: a comprehensive description of the temporal evolution of GaN nanowire ensembles.

We use line-of-sight quadrupole mass spectrometry to monitor the spontaneous formation of GaN nanowires on Si during molecular beam epitaxy. We find that the temporal evolution of nanowire ensembles is well described by a double logistic function. The analysis of the temporal evolution of nanowire ensembles, prepared under a wide variety of growth conditions, allows us to construct a growth diagram that can be used to predict the average delay time that precedes nanowire formation.

Compatibility of the selective area growth of GaN nanowires on AlN-buffered Si substrates with the operation of light emitting diodes

AlN layers with thicknesses between 2 and 14 nm were grown on Si(111) substrates by molecular beam epitaxy. The effect of the AlN layer thickness on the morphology and nucleation time of spontaneously formed GaN nanowires (NWs) was investigated by scanning electron microscopy and line-of-sight quadrupole mass spectrometry, respectively. We observed that the alignment of the NWs grown on these layers improves with increasing layer thickness while their nucleation time decreases. Our results show that 4 nm is the smallest thickness of the AlN layer that allows the growth of well-aligned NWs with short nucleation time. Such an AlN buffer layer was successfully employed, together with a patterned SiOx mask, for the selective-area growth (SAG) of vertical GaN NWs. In addition, we fabricated light-emitting diodes (LEDs) from NW ensembles that were grown by means of self-organization phenomena on bare and on AlN-buffered Si substrates. A careful characterization of the optoelectronic properties of the two devices showed that the performance of NW-LEDs on bare and AlN-buffered Si is similar. Electrical conduction across the AlN buffer is facilitated by a high number of grain boundaries that were revealed by transmission electron microscopy. These results demonstrate that grainy AlN buffer layers on Si are compatible both with the SAG of GaN NWs and LED operation. Therefore, this study is a first step towards the fabrication of LEDs on Si substrates based on homogeneous NW ensembles.

Non-destructive assessment of the polarity of GaN nanowire ensembles using low-energy electron diffraction and x-ray photoelectron diffraction

We investigate GaN nanowire ensembles spontaneously formed in plasma-assisted molecular beam epitaxy by non-destructive low-energy electron diffraction (LEED) and x-ray photoelectron diffraction (XPD). We show that GaN nanowire ensembles prepared on AlN-buffered 6H-SiC(0001¯) substrates with well-defined N polarity exhibit similar LEED intensity-voltage curves and angular distribution of photo-emitted electrons as N-polar free-standing GaN layers. Therefore, as in the case of GaN layers, LEED and XPD are found to be suitable techniques to assess the polarity of GaN nanowire ensembles on a macroscopic scale. The analysis of GaN nanowire ensembles prepared on bare Si(111) allows us to conclude that, on this non-polar substrate, the majority of nanowires is also N-polar.

Mass-transport driven growth dynamics of AlGaAs shells deposited around dense GaAs nanowires by metalorganic vapor phase epitaxy

The MOVPE growth dynamics of AlGaAs shell material around ensembles of free-standing GaAs nanowires is presented and described by a model based on the vapor mass-transport of group-III species and the nanowires relevant size (diameter, height) and density.

Controlled Pore Formation on Mesoporous Single Crystalline Silicon Nanowires: Threshold and Mechanisms

Silicon nanowires are prepared by the method of the two‐step metal‐assisted wet chemical etching. We analyzed the structure of solid, rough, and porous nanowire surfaces of boron‐doped silicon substrates with resistivities of ρ > 1000 Ωcm, ρ = 14–23 Ωcm, and ρ < 0.01 Ωcm by scanning electron microscopy and nitrogen gas adsorption. Silicon nanowires prepared from highly doped silicon reveal mesopores on their surface. However, we found a limit for pore formation. Pores were only formed by etching below a critical H2O2 concentration ( M). Furthermore, we determined the pore size distribution dependent on the etching parameters and characterized the morphology of the pores on the nanowire surface. The pores are in the regime of small mesopores with a mean diameter of 9–13 nm. Crystal and surface structure of individual mesoporous nanowires were investigated by transmission electron microscopy. The vibrational properties of nanowire ensembles were investigated by Raman spectroscopy. Heavily boron‐doped silicon nanowires are highly porous and the remaining single crystalline silicon nanoscale mesh leads to a redshift and a strong asymmetric line broadening for Raman scattering by optical phonons at 520 cm−1. This redshift, λSi bulk = 520 cm−1 →λSi nanowire = 512 cm−1, hints to a phonon confinement in mesoporous single crystalline silicon nanowires.

Silver catalyzed growth of InxGa1−xAs nanowires on Si(001) by metal–organic chemical vapor deposition

We report the growth of InxGa1−xAs nanowires on Si(100) substrates by the metal–organic chemical vapor deposition technique in a one-step process using silver nanoparticles as catalysts. Nanowires were found to grow below the eutectic temperature of Ag–Si over a wide range of temperature. The morphology and mode of nanowire growth were found to change with growth temperature. The images obtained from field-emission scanning electron microscopy reveal that growth at 600 °C promotes multi-prong nanowires, while nanowires grown at a lower temperature are single-prong. The effect of temperature on the growth of nanowires was explained with the help of a model developed on the basis of classical nucleation theory. X-ray photoelectron spectroscopic measurements validate the growth of InxGa1−xAs nanowires on Si. A pure zinc blende phase, free from stacking defects, is observed from high-resolution transmission electron microscopy images and the associated indexed selected area electron diffraction patterns. The optical bandgap energy of the nanowire ensemble was calculated by diffused reflectance spectroscopy. Compositional mapping using energy dispersive X-ray spectroscopy shows uniform distribution of three constituent elements along the length of the nanowires. Our study gives new insights into the particle-assisted growth mechanism of III–V compound nanowires and promotes the use of Ag nanoparticles as catalysts as a better option over gold nanoparticles which will eventually help in integrating III–V nanostructures with existing silicon microelectronics to pave the way for photonic devices on silicon.