Uniform large-area surface patterning achieved by metal dewetting for the top-down fabrication of GaN nanowire ensembles.

The dewetting of thin Pt films on different surfaces is investigated as a means to provide the patterning for the top-down fabrication of GaN nanowire ensembles. The transformation from a thin film to an ensemble of nanoislands upon annealing proceeds in good agreement with the void growth model. With increasing annealing duration, the size and shape uniformity of the nanoislands improves. This improvement speeds up for higher annealing temperature. After an optimum annealing duration, the size uniformity deteriorates due to the coalescence of neighboring islands. By changing the Pt film thickness, the nanoisland diameter and density can be quantitatively controlled in a way predicted by a simple thermodynamic model. We demonstrate the uniformity of the nanoisland ensembles for an area larger than 1 cm2. GaN nanowires are fabricated by a sequence of dry and wet etching steps, and these nanowires inherit the diameters and density of the Pt nanoisland ensemble used as a mask. Our study achieves advancements in size uniformity and range of obtainable diameters compared to previous works. This simple, economical, and scalable approach to the top-down fabrication of nanowires is useful for applications requiring large and uniform nanowire ensembles with controllable dimensions.

ScN/GaN(11Ì 00): A New Platform for the Epitaxy of Twin-Free Metal-Semiconductor Heterostructures.

We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11̅00) surface. To this end, ScN is grown on freestanding GaN(11̅00) substrates and self-assembled GaN nanowires exhibiting (11̅00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]∥GaN(11̅00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11̅00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.

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

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

Growth mechanisms in molecular beam epitaxy for GaN-(In,Ga)N core-shell nanowires emitting in the green spectral range.

Using molecular beam epitaxy, we demonstrate the growth of (In,Ga)N shells emitting in the green spectral range around very thin (35 nm diameter) GaN core nanowires. These GaN nanowires are obtained by self-assembled growth on TiN. We present a qualitative shell growth model accounting for both the three-dimensional nature of the nanostructures as well as the directionality of the atomic fluxes. This model allows us, on the one hand, to optimise the conditions for high and homogeneous In incorporation and, on the other hand, to explain the influence of changes in the growth conditions on the sample morphology and In content. Specifically, the impact of the V/III and In/Ga flux ratios, the rotation speed and the rotation direction are investigated. Notably, with In acting as surfactant, the ternary (In,Ga)N shells are much more homogeneous in thickness along the nanowire length than their binary GaN counterparts.

Near-infrared emission from spatially indirect excitons in type II ZnTe/CdSe/(Zn,Mg)Te core/double-shell nanowires.

ZnTe/CdSe/(Zn, Mg)Te core/double-shell nanowires are grown by molecular beam epitaxy by employing the vapor-liquid-solid growth mechanism assisted with gold catalysts. A photoluminescence study of these structures reveals the presence of an optical emission in the near infrared. We assign this emission to the spatially indirect exciton recombination at the ZnTe/CdSe type II interface. This conclusion is confirmed by the observation of a significant blue-shift of the emission energy with an increasing excitation fluence induced by the electron-hole separation at the interface. Cathodoluminescence measurements reveal that the optical emission in the near infrared originates from nanowires and not from two-dimensional residual deposits between them. Moreover, it is demonstrated that the emission energy in the near infrared depends on the average CdSe shell thickness and the average Mg concentration within the (Zn, Mg)Te shell. The main mechanism responsible for these changes is associated with the strain induced by the (Zn, Mg)Te shell in the entire core/shell nanowire heterostructure.

Beam damage of single semiconductor nanowires during X-ray nanobeam diffraction experiments.

Nanoprobe X-ray diffraction (nXRD) using focused synchrotron radiation is a powerful technique to study the structural properties of individual semiconductor nanowires. However, when performing the experiment under ambient conditions, the required high X-ray dose and prolonged exposure times can lead to radiation damage. To unveil the origin of radiation damage, a comparison is made of nXRD experiments carried out on individual semiconductor nanowires in their as-grown geometry both under ambient conditions and under He atmosphere at the microfocus station of the P08 beamline at the third-generation source PETRA III. Using an incident X-ray beam energy of 9 keV and photon flux of 1010 s-1, the axial lattice parameter and tilt of individual GaAs/In0.2Ga0.8As/GaAs core-shell nanowires were monitored by continuously recording reciprocal-space maps of the 111 Bragg reflection at a fixed spatial position over several hours. In addition, the emission properties of the (In,Ga)As quantum well, the atomic composition of the exposed nanowires and the nanowire morphology were studied by cathodoluminescence spectroscopy, energy-dispersive X-ray spectroscopy and scanning electron microscopy, respectively, both prior to and after nXRD exposure. Nanowires exposed under ambient conditions show severe optical and morphological damage, which was reduced for nanowires exposed under He atmosphere. The observed damage can be largely attributed to an oxidation process from X-ray-induced ozone reactions in air. Due to the lower heat-transfer coefficient compared with GaAs, this oxide shell limits the heat transfer through the nanowire side facets, which is considered as the main channel of heat dissipation for nanowires in the as-grown geometry.

Correlated and in-situ electrical transmission electron microscopy studies and related membrane-chip fabrication.

Understanding the interplay between the structure, composition and opto-electronic properties of semiconductor nano-objects requires combining transmission electron microscopy (TEM) based techniques with electrical and optical measurements on the very same specimen. Recent developments in TEM technologies allow not only the identification and in-situ electrical characterization of a particular object, but also the direct visualization of its modification in-situ by techniques such as Joule heating. Over the past years, we have carried out a number of studies in these fields that are reviewed in this contribution. In particular, we discuss here i) correlated studies where the same unique object is characterized electro-optically and by TEM, ii) in-situ Joule heating studies where a solid-state metal-semiconductor reaction is monitored in the TEM, and iii) in-situ biasing studies to better understand the electrical properties of contacted single nanowires. In addition, we provide detailed fabrication steps for the silicon nitride membrane-chips crucial to these correlated and in-situ measurements.

Electroluminescence and current-voltage measurements of single-(In,Ga)N/GaN-nanowire light-emitting diodes in a nanowire ensemble.

We present the combined analysis of electroluminescence (EL) and current-voltage (I-V) behavior of single, freestanding (In,Ga)N/GaN nanowire (NW) light-emitting diodes (LEDs) in an unprocessed, self-assembled ensemble grown by molecular beam epitaxy. The data were acquired in a scanning electron microscope equipped with a micromanipulator and a luminescence detection system. Single NW spectra consist of emission lines originating from different quantum wells, and the width of the spectra increases with decreasing peak emission energy. The corresponding I-V characteristics are described well by a modified Shockley equation. The key advantage of this measurement approach is the possibility to correlate the EL intensity of a single-NW LED with the actual current density in this NW. This way, the external quantum efficiency (EQE) can be investigated as a function of the current in a single-NW LED. The comparison of the EQE characteristic of single NWs and the ensemble device allows for a quite accurate determination of the actual number of emitting NWs in the working ensemble LED and the respective current densities in its individual NWs. This information is decisive for a meaningful and comprehensive characterization of a NW ensemble device, rendering the measurement approach employed here a very powerful analysis tool.

Correlated Nanoscale Analysis of the Emission from Wurtzite versus Zincblende (In,Ga)As/GaAs Nanowire Core-Shell Quantum Wells.

While the properties of wurtzite GaAs have been extensively studied during the past decade, little is known about the influence of the crystal polytype on ternary (In,Ga)As quantum well structures. We address this question with a unique combination of correlated, spatially resolved measurement techniques on core-shell nanowires that contain extended segments of both the zincblende and wurtzite polytypes. Cathodoluminescence hyperspectral imaging reveals a blue-shift of the quantum well emission energy by 75 ± 15 meV in the wurtzite polytype segment. Nanoprobe X-ray diffraction and atom probe tomography enable k·p calculations for the specific sample geometry to reveal two comparable contributions to this shift. First, there is a 30% drop in In mole fraction going from the zincblende to the wurtzite segment. Second, the quantum well is under compressive strain, which has a much stronger impact on the hole ground state in the wurtzite than in the zincblende segment. Our results highlight the role of the crystal structure in tuning the emission of (In,Ga)As quantum wells and pave the way to exploit the possibilities of three-dimensional band gap engineering in core-shell nanowire heterostructures. At the same time, we have demonstrated an advanced characterization toolkit for the investigation of semiconductor nanostructures.

Top-down fabrication of ordered arrays of GaN nanowires by selective area sublimation.

We demonstrate the top-down fabrication of ordered arrays of GaN nanowires by selective area sublimation of pre-patterned GaN(0001) layers grown by hydride vapor phase epitaxy on Al2O3. Arrays with nanowire diameters and spacings ranging from 50 to 90 nm and 0.1 to 0.7 µm, respectively, are simultaneously produced under identical conditions. The sublimation process, carried out under high vacuum conditions, is analyzed in situ by reflection high-energy electron diffraction and line-of-sight quadrupole mass spectrometry. During the sublimation process, the GaN(0001) surface vanishes, giving way to the formation of semi-polar {11̄03} facets which decompose congruently following an Arrhenius temperature dependence with an activation energy of (3.54 ± 0.07) eV and an exponential prefactor of 1.58 × 1031 atoms per cm2 per s. The analysis of the samples by low-temperature cathodoluminescence spectroscopy reveals that, in contrast to dry etching, the sublimation process does not introduce nonradiative recombination centers at the nanowire sidewalls. This technique is suitable for the top-down fabrication of a variety of ordered nanostructures, and could possibly be extended to other material systems with similar crystallographic properties such as ZnO.

Near- and mid-infrared intersubband absorption in top-down GaN/AlN nano- and micro-pillars.

We present a systematic study of top-down processed GaN/AlN heterostructures for intersubband optoelectronic applications. Samples containing quantum well superlattices that display either near- or mid-infrared intersubband absorption were etched into nano- and micro-pillar arrays in an inductively coupled plasma. We investigate the influence of this process on the structure and strain-state, on the interband emission and on the intersubband absorption. Notably, for pillar spacings significantly smaller (≤1/3) than the intersubband wavelength, the magnitude of the intersubband absorption is not reduced even when 90% of the material is etched away and a similar linewidth is obtained. The same holds for the interband emission. In contrast, for pillar spacings on the order of the intersubband absorption wavelength, the intersubband absorption is masked by refraction effects and photonic crystal modes. The presented results are a first step towards micro- and nano-structured group-III nitride devices relying on intersubband transitions.

Effect of the nanowire diameter on the linearity of the response of GaN-based heterostructured nanowire photodetectors.

Nanowire photodetectors are investigated because of their compatibility with flexible electronics, or for the implementation of on-chip optical interconnects. Such devices are characterized by ultrahigh photocurrent gain, but their photoresponse scales sublinearly with the optical power. Here, we present a study of single-nanowire photodetectors displaying a linear response to ultraviolet illumination. Their structure consists of a GaN nanowire incorporating an AlN/GaN/AlN heterostructure, which generates an internal electric field. The activity of the heterostructure is confirmed by the rectifying behavior of the current-voltage characteristics in the dark, as well as by the asymmetry of the photoresponse in magnitude and linearity. Under reverse bias (negative bias on the GaN cap segment), the detectors behave linearly with the impinging optical power when the nanowire diameter is below a certain threshold (≈80 nm), which corresponds to the total depletion of the nanowire stem due to the Fermi level pinning at the sidewalls. In the case of nanowires that are only partially depleted, their nonlinearity is explained by a nonlinear variation of the diameter of their central conducting channel under illumination.

Metal-Exchange Catalysis in the Growth of Sesquioxides: Towards Heterostructures of Transparent Oxide Semiconductors.

We observe that the growth rate of Ga_{2}O_{3} in plasma-assisted molecular beam epitaxy can be drastically enhanced by an additional In supply. This enhancement is shown to result from a catalytic effect, namely, the rapid formation of In_{2}O_{3}, immediately followed by a transformation of In_{2}O_{3} to Ga_{2}O_{3} due to an In-Ga interatomic exchange. We derive a simple model that quantitatively describes this process as well as its consequences on the formation rate of Ga_{2}O_{3}. Moreover, we demonstrate that the catalytic action of In_{2}O_{3} allows the synthesis of the metastable hexagonal phase of Ga_{2}O_{3}. Since the Ga_{2}O_{3}(0001)/In_{2}O_{3}(111) interface is closely lattice matched, this novel growth mode opens a new path for the fabrication of sesquioxide heterostructures.

Near-Infrared Intersubband Photodetection in GaN/AlN Nanowires.

Intersubband optoelectronic devices rely on transitions between quantum-confined electron levels in semiconductor heterostructures, which enables infrared (IR) photodetection in the 1-30 µm wavelength window with picosecond response times. Incorporating nanowires as active media could enable an independent control over the electrical cross-section of the device and the optical absorption cross-section. Furthermore, the three-dimensional carrier confinement in nanowire heterostructures opens new possibilities to tune the carrier relaxation time. However, the generation of structural defects and the surface sensitivity of GaAs nanowires have so far hindered the fabrication of nanowire intersubband devices. Here, we report the first demonstration of intersubband photodetection in a nanowire, using GaN nanowires containing a GaN/AlN superlattice absorbing at 1.55 µm. The combination of spectral photocurrent measurements with 8-band k·p calculations of the electronic structure supports the interpretation of the result as intersubband photodetection in these extremely short-period superlattices. We observe a linear dependence of the photocurrent with the incident illumination power, which confirms the insensitivity of the intersubband process to surface states and highlights how architectures featuring large surface-to-volume ratios are suitable as intersubband photodetectors. Our analysis of the photocurrent characteristics points out routes for an improvement of the device performance. This first nanowire based intersubband photodetector represents a technological breakthrough that paves the way to a powerful device platform with potential for ultrafast, ultrasensitive photodetectors and highly efficient quantum cascade emitters with improved thermal stability.

Bias-Controlled Spectral Response in GaN/AlN Single-Nanowire Ultraviolet Photodetectors.

We present a study of GaN single-nanowire ultraviolet photodetectors with an embedded GaN/AlN superlattice. The heterostructure dimensions and doping profile were designed in such a way that the application of positive or negative bias leads to an enhancement of the collection of photogenerated carriers from the GaN/AlN superlattice or from the GaN base, respectively, as confirmed by electron beam-induced current measurements. The devices display enhanced response in the ultraviolet A (≈ 330-360 nm)/B (≈ 280-330 nm) spectral windows under positive/negative bias. The result is explained by correlation of the photocurrent measurements with scanning transmission electron microscopy observations of the same single nanowire and semiclassical simulations of the strain and band structure in one and three dimensions.

Quenching of the luminescence intensity of GaN nanowires under electron beam exposure: impact of C adsorption on the exciton lifetime.

Electron irradiation of GaN nanowires in a scanning electron microscope strongly reduces their luminous efficiency as shown by cathodoluminescence imaging and spectroscopy. We demonstrate that this luminescence quenching originates from a combination of charge trapping at already existing surface states and the formation of new surface states induced by the adsorption of C on the nanowire sidewalls. The interplay of these effects leads to a complex temporal evolution of the quenching, which strongly depends on the incident electron dose per area. Time-resolved photoluminescence measurements on electron-irradiated samples reveal that the carbonaceous adlayer affects both the nonradiative and the radiative recombination dynamics.

UV Photosensing Characteristics of Nanowire-Based GaN/AlN Superlattices.

We have characterized the photodetection capabilities of single GaN nanowires incorporating 20 periods of AlN/GaN:Ge axial heterostructures enveloped in an AlN shell. Transmission electron microscopy confirms the absence of an additional GaN shell around the heterostructures. In the absence of a surface conduction channel, the incorporation of the heterostructure leads to a decrease of the dark current and an increase of the photosensitivity. A significant dispersion in the magnitude of dark currents for different single nanowires is attributed to the coalescence of nanowires with displaced nanodisks, reducing the effective length of the heterostructure. A larger number of active nanodisks and AlN barriers in the current path results in lower dark current and higher photosensitivity and improves the sensitivity of the nanowire to variations in the illumination intensity (improved linearity). Additionally, we observe a persistence of the photocurrent, which is attributed to a change of the resistance of the overall structure, particularly the GaN stem and cap sections. As a consequence, the time response is rather independent of the dark current.

Radial Stark Effect in (In,Ga)N Nanowires.

We study the luminescence of unintentionally doped and Si-doped InxGa1-xN nanowires with a low In content (x < 0.2) grown by molecular beam epitaxy on Si substrates. The emission band observed at 300 K from the unintentionally doped samples is centered at much lower energies (800 meV) than expected from the In content measured by X-ray diffractometry and energy dispersive X-ray spectroscopy. This discrepancy arises from the pinning of the Fermi level at the sidewalls of the nanowires, which gives rise to strong radial built-in electric fields. The combination of the built-in electric fields with the compositional fluctuations inherent to (In,Ga)N alloys induces a competition between spatially direct and indirect recombination channels. At elevated temperatures, electrons at the core of the nanowire recombine with holes close to the surface, and the emission from unintentionally doped nanowires exhibits a Stark shift of several hundreds of meV. The competition between spatially direct and indirect transitions is analyzed as a function of temperature for samples with various Si concentrations. We propose that the radial Stark effect is responsible for the broadband absorption of (In,Ga)N nanowires across the entire visible range, which makes these nanostructures a promising platform for solar energy applications.

Photoelectrochemical properties of (In,Ga)N nanowires for water splitting investigated by in situ electrochemical mass spectroscopy.

We investigated the photoelectrochemical properties of both n- and p-type (In,Ga)N nanowires (NWs) for water splitting by in situ electrochemical mass spectroscopy (EMS). All NWs were prepared by plasma-assisted molecular beam epitaxy. Under illumination, the n-(In,Ga)N NWs exhibited an anodic photocurrent, however, no O2 but only N2 evolution was detected by EMS, indicating that the photocurrent was related to photocorrosion rather than water oxidation. In contrast, the p-(In,Ga)N NWs showed a cathodic photocurrent under illumination which was correlated with the evolution of H2. After photodeposition of Pt on such NWs, the photocurrent density was significantly enhanced to 5 mA/cm(2) at a potential of -0.5 V/NHE under visible light irradiation of ∼40 mW/cm(2). Also, incident photon-to-current conversion efficiencies of around 40% were obtained at -0.45 V/NHE across the entire visible spectral region. The stability of the NW photocathodes for at least 60 min was verified by EMS. These results suggest that p-(In,Ga)N NWs are a promising basis for solar hydrogen production.

Epitaxial interfaces between crystallographically mismatched materials.

We report an unexpected mechanism by which an epitaxial interface can form between materials having strongly mismatched lattice constants. A simple model is proposed in which one material tilts out of the interface plane to create a coincidence-site lattice that balances two competing geometrical criteria--low residual strain and short coincidence-lattice period. We apply this model, along with complementary first-principles total-energy calculations, to the interface formed by molecular-beam epitaxy of cubic Fe on hexagonal GaN and find excellent agreement between theory and experiment.