Effect of Extended Defects on AlGaN Quantum Dots for Electron-Pumped Ultraviolet Emitters.

We study the origin of bimodal emission in AlGaN/AlN QD superlattices displaying a high internal quantum efficiency (around 50%) in the 230-300 nm spectral range. The secondary emission at longer wavelengths is linked to the presence of cone-like domains with deformed QD layers, which originate at the first AlN buffer/superlattice interface and propagate vertically. The cones originate at a 30°-faceted shallow pit in the AlN, which appears to be associated with a threading dislocation that produces strong shear strain. The cone-like structures present Ga enrichment at the boundaring facets and larger QDs within the conic domain. The bimodality of the luminescence is attributed to the differing dot size and composition within the cones and at the faceted boundaries, which is confirmed by the correlation of microscopy results and Schrödinger-Poisson calculations.

Long indium-rich InGaAs nanowires by SAG-HVPE.

We demonstrate the selective area growth of InGaAs nanowires (NWs) on GaAs (111)B substrates using hydride vapor phase epitaxy (HVPE). A high growth rate of more than 50µm h-1and high aspect ratio NWs were obtained. Composition along the NWs was investigated by energy dispersive x-ray spectroscopy giving an average indium composition of 84%. This is consistent with the composition of 78% estimated from the photoluminescence spectrum of the NWs. Crystal structure analysis of the NWs by transmission electron microscopy indicated random stacking faults related to zinc-blende/wurtzite polytypism. This work demonstrates the ability of HVPE for growing high aspect ratio InGaAs NW arrays.

Optical net gain measurement on Al0.07Ga0.93N/GaN multi-quantum wells.

We report net gain measurements at room temperature in Al0.07Ga0.93N/GaN 10-period multi-quantum well layers emitting at 367 nm, using the variable stripe length method. The separate confinement heterostructure was designed targeting electron-beam pumped lasing at 10 kV. The highest net gain value was 131 cm-1, obtained at the maximum pumping power density of the experimental setup (743 kW/cm2). The net gain threshold was attained at 218 kW/cm2 using 193 nm optical pumping. From these experiments, we predict an electron-beam-pumped lasing threshold of 370 kW/cm2 at room temperature, which is compatible with the use of compact cathodes (e.g. carbon nanotubes). In some areas of the sample, we observed an anomalous amplification of the photoluminescence intensity that occurs for long stripe lengths (superior to 400 µm) and high pumping power (superior to 550 kW/cm2), leading to an overestimation of the net gain value. We attribute such a phenomenon to the optical feedback provided by the reflection from cracks, which were created during the epitaxial growth due to the strong lattice mismatch between different layers.

AlGaN/GaN asymmetric graded-index separate confinement heterostructures designed for electron-beam pumped UV lasers.

We present a study of undoped AlGaN/GaN separate confinement heterostructures designed to operate as electron beam pumped ultraviolet lasers. We discuss the effect of spontaneous and piezoelectric polarization on carrier diffusion, comparing the results of cathodoluminescence with electronic simulations of the band structure and Monte Carlo calculations of the electron trajectories. Carrier collection is significantly improved using an asymmetric graded-index separate confinement heterostructure (GRINSCH). The graded layers avoid potential barriers induced by polarization differences in the heterostructure and serve as strain transition buffers which reduce the mosaicity of the active region and the linewidth of spontaneous emission.

Solubility Limit of Ge Dopants in AlGaN: A Chemical and Microstructural Investigation Down to the Nanoscale.

Attaining low-resistivity AlxGa1-xN layers is one keystone to improve the efficiency of light-emitting devices in the ultraviolet spectral range. Here, we present a microstructural analysis of AlxGa1-xN/Ge samples with 0 ≤ x ≤ 1, and a nominal doping level in the range of 1020 cm-3, together with the measurement of Ge concentration and its spatial distribution down to the nanometer scale. AlxGa1-xN/Ge samples with x ≤ 0.2 do not present any sign of inhomogeneity. However, samples with x > 0.4 display µm-size Ge crystallites at the surface. Ge segregation is not restricted to the surface: Ge-rich regions with a size of tens of nanometers are observed inside the AlxGa1-xN/Ge layers, generally associated with Ga-rich regions around structural defects. With these local exceptions, the AlxGa1-xN/Ge matrix presents a homogeneous Ge composition which can be significantly lower than the nominal doping level. Precise measurements of Ge in the matrix provide a view of the solubility diagram of Ge in AlxGa1-xN as a function of the Al mole fraction. The solubility of Ge in AlN is extremely low. Between AlN and GaN, the solubility increases linearly with the Ga mole fraction in the ternary alloy, which suggests that the Ge incorporation takes place by substitution of Ga atoms only. The maximum percentage of Ga sites occupied by Ge saturates around 1%. The solubility issues and Ge segregation phenomena at different length scales likely play a role in the efficiency of Ge as an n-type AlGaN dopant, even at Al concentrations where Ge DX centers are not expected to manifest. Therefore, this information can have direct impact on the performance of Ge-doped AlGaN light-emitting diodes, particularly in the spectral range for disinfection (≈260 nm), which requires heavily doped alloys with a high Al mole fraction.

Comprehensive model toward optimization of SAG In-rich InGaN nanorods by hydride vapor phase epitaxy.

Controlled growth of In-rich InGaN nanowires/nanorods (NRs) has long been considered as a very challenging task. Here, we present the first attempt to fabricate InGaN NRs by selective area growth using hydride vapor phase epitaxy. It is shown that InGaN NRs with different indium contents up to 90% can be grown by varying the In/Ga flow ratio. Furthermore, nanowires are observed on the surface of the grown NRs with a density that is proportional to the Ga content. The impact of varying the NH3 partial pressure is investigated to suppress the growth of these nanowires. It is shown that the nanowire density is considerably reduced by increasing the NH3 content in the vapor phase. We attribute the emergence of the nanowires to the final step of growth occurring after stopping the NH3 flow and cooling down the substrate. This is supported by a theoretical model based on the calculation of the supersaturation of the ternary InGaN alloy in interaction with the vapor phase as a function of different parameters assessed at the end of growth. It is shown that the decomposition of the InGaN solid alloy indeed becomes favorable below a critical value of the NH3 partial pressure. The time needed to reach this value increases with increasing the input flow of NH3, and therefore the alloy decomposition leading to the formation of nanowires becomes less effective. These results should be useful for fundamental understanding of the growth of InGaN nanostructures and may help to control their morphology and chemical composition required for device applications.

The role of surface diffusion in the growth mechanism of III-nitride nanowires and nanotubes.

The spontaneous growth of GaN nanowires (NWs) in absence of catalyst is controlled by the Ga flux impinging both directly on the top and on the side walls and diffusing to the top. The presence of diffusion barriers on the top surface and at the frontier between the top and the sidewalls, however, causes an inhomogeneous distribution of Ga adatoms at the NW top surface resulting in a GaN accumulation in its periphery. The increased nucleation rate in the periphery promotes the spontaneous formation of superlattices in InGaN and AlGaN NWs. In the case of AlN NWs, the presence of Mg can enhance the otherwise short Al diffusion length along the sidewalls inducing the formation of AlN nanotubes.

Growth of zinc-blende GaN on muscovite mica by molecular beam epitaxy.

The mechanisms of plasma-assisted molecular beam epitaxial growth of GaN on muscovite mica were investigated. Using a battery of techniques, including scanning and transmission electron microscopy, atomic force microscopy, cathodoluminescence, Raman spectroscopy and x-ray diffraction, it was possible to establish that, in spite of the lattice symmetry mismatch, GaN grows in epitaxial relationship with mica, with the [11-20] GaN direction parallel to [010] direction of mica. GaN layers could be easily detached from the substrate via the delamination of the upper layers of the mica itself, discarding the hypothesis of a van der Waals growth mode. Mixture of wurtzite (hexagonal) and zinc blende (ZB) (cubic) crystallographic phases was found in the GaN layers with ratios highly dependent on the growth conditions. Interestingly, almost pure ZB GaN epitaxial layers could be obtained at high growth temperature, suggesting the existence of a specific GaN nucleation mechanism on mica and opening a new way to the growth of the thermodynamically less stable ZB GaN phase.

UV Emission from GaN Wires with m-Plane Core-Shell GaN/AlGaN Multiple Quantum Wells.

The present work reports high-quality nonpolar GaN/Al0.6Ga0.4N multiple quantum wells (MQWs) grown in core-shell geometry by metal-organic vapor-phase epitaxy on the m-plane sidewalls of c̅-oriented hexagonal GaN wires. Optical and structural studies reveal ultraviolet (UV) emission originating from the core-shell GaN/AlGaN MQWs. Tuning the m-plane GaN QW thickness from 4.3 to 0.7 nm leads to a shift of the emission from 347 to 292 nm, consistent with Schrödinger-Poisson calculations. The evolution of the luminescence with temperature displays signs of strong localization, especially for samples with thinner GaN QWs and no evidence of quantum-confined Stark effect, as expected for nonpolar m-plane surfaces. The internal quantum efficiency derived from the photoluminescence (PL) intensity ratio at low and room temperatures is maximum (∼7.3% measured at low power excitation) for 2.6 nm thick quantum wells, emitting at 325 nm, and shows a large drop for thicker QWs. An extensive study of the PL quenching with temperature is presented. Two nonradiative recombination paths are activated at different temperatures. The low-temperature path is found to be intrinsic to the heterostructure, whereas the process that dominates at high temperature depends on the QW thickness and is strongly enhanced for QWs larger than 2.6 nm, causing a rapid decrease in the internal quantum efficiency.

Role of Underlayer for Efficient Core-Shell InGaN QWs Grown on m-plane GaN Wire Sidewalls.

Different types of buffer layers such as InGaN underlayer (UL) and InGaN/GaN superlattices are now well-known to significantly improve the efficiency of c-plane InGaN/GaN-based light-emitting diodes (LEDs). The present work investigates the role of two different kinds of pregrowth layers (low In-content InGaN UL and GaN UL namely "GaN spacer") on the emission of the core-shell m-plane InGaN/GaN single quantum well (QW) grown around Si-doped c̅-GaN microwires obtained by silane-assisted metal organic vapor phase epitaxy. According to photo- and cathodoluminescence measurements performed at room temperature, an improved efficiency of light emission at 435 nm with internal quantum efficiency >15% has been achieved by adding a GaN spacer prior to the growth of QW. As revealed by scanning transmission electron microscopy, an ultrathin residual layer containing Si located at the wire sidewall surfaces favors the formation of high density of extended defects nucleated at the first InGaN QW. This contaminated residual incorporation is buried by the growth of the GaN spacer and avoids the structural defect formation, therefore explaining the improved optical efficiency. No further improvement is observed by adding the InGaN UL to the structure, which is confirmed by comparable values of the effective carrier lifetime estimated from time-resolved experiments. Contrary to the case of planar c-plane QW where the improved efficiency is attributed to a strong decrease of point defects, the addition of an InGaN UL seems to have no influence in the case of radial m-plane QW.

Correlative investigation of Mg doping in GaN layers grown at different temperatures by atom probe tomography and off-axis electron holography.

Correlation between off-axis electron holography and atom probe tomography (APT) provides morphological, chemical and electrical information about Mg doping (p-type) in gallium nitride (GaN) layers that have been grown at different temperatures at a nanometric scale. APT allows access to the three-dimensional distribution of atoms and their chemical nature. In particular, this technique allows visualisation of the Mg-rich clusters observed in p-doped GaN layers grown by metal-organic chemical vapour deposition. As the layer growth temperature increases, the cluster density decreases but their size indicted by the number of atoms increases. Moreover, APT reveals that threading dislocations are decorated with Mg atoms. Off-axis electron holography provides complementary information about the electrical activity of the Mg doping. As only a small fraction of dopant atoms are ionised at room temperature, this fraction is increased by annealing the specimen to 400 °C in situ in a transmission electron microscope (TEM). A strong reduction of the dopant electrical activity is observed for increases in the layer growth temperature. The correlation of APT with TEM-based techniques was shown to be a unique approach in order to investigate how the growth temperature affects both the chemical distribution and electrical activity of Mg dopant atoms.

High Lateral Breakdown Voltage in Thin Channel AlGaN/GaN High Electron Mobility Transistors on AlN/Sapphire Templates.

In this paper, we present the fabrication and Direct Current/high voltage characterizations of AlN-based thin and thick channel AlGaN/GaN heterostructures that are regrown by molecular beam epitaxy on AlN/sapphire. A very high lateral breakdown voltage above 10 kV was observed on the thin channel structure for large contact distances. Also, the buffer assessment revealed a remarkable breakdown field of 5 MV/cm for short contact distances, which is far beyond the theoretical limit of the GaN-based material system. The potential interest of the thin channel configuration in AlN-based high electron mobility transistors is confirmed by the much lower breakdown field that is obtained on the thick channel structure. Furthermore, fabricated transistors are fully functional on both structures with low leakage current, low on-resistance, and reduced temperature dependence as measured up to 300 °C. This is attributed to the ultra-wide bandgap AlN buffer, which is extremely promising for high power, high temperature future applications.

Si Doping of Vapor-Liquid-Solid GaAs Nanowires: n-Type or p-Type?

The incorporation of Si into vapor-liquid-solid GaAs nanowires often leads to p-type doping, whereas it is routinely used as an n-dopant of planar layers. This property limits the applications of GaAs nanowires in electronic and optoelectronic devices. The strong amphoteric behavior of Si in nanowires is not yet fully understood. Here, we present the first attempt to quantify this behavior as a function of the droplet composition and temperature. It is shown that the doping type critically depends on the As/Ga ratio in the droplet. In sharp contrast to vapor-solid growth, the droplet contains very few As atoms, which enhance their reverse transfer from solid to liquid. As a result, Si atoms preferentially replace As in GaAs, leading to p-type doping in nanowires. Hydride vapor phase epitaxy provides the highest As concentrations in the catalyst droplets during their vapor-liquid-solid growth, resulting in n-type dopant behavior of Si. We present experimental data on n-doped Si-doped GaAs nanowires grown by this method and explain the doping within our model. These results give a clear route for obtaining n-type or p-type Si doping in GaAs nanowires and may be extended to other III-V nanowires.

Compositional control of homogeneous InGaN nanowires with the In content up to 90.

Homogenous InGaN nanowires with a controlled indium composition up to 90% are grown on GaN/c-Al2O3 templates by catalyst-free hydride vapor phase epitaxy using InCl3 and GaCl as group III element precursors. The influence of the partial pressures on the growth rate and composition of InGaN nanowires is investigated. It is shown how the InN mole fraction in nanowires can be finely tuned by changing the vapor phase composition. Thermodynamic calculations are presented that take into account different interconnected reactions in the vapor phase and show a good agreement with the compositional data. Energy dispersive x-ray spectroscopy profiles performed on single nanowires show a homogenous indium composition along the entire nanowire length. X-ray diffraction measurements performed on nanowires arrays confirm these data. High-resolution transmission electron microscopy analysis shows the wurtzite crystal structure with a reduced defect density for InGaN nanowires with the highest indium content.

Circumventing the miscibility gap in InGaN nanowires emitting from blue to red.

Widegap III-nitride alloys have enabled new classes of optoelectronic devices including light emitting diodes, lasers and solar cells, but it is admittedly challenging to extend their operating wavelength to the yellow-red band. This requires an increased In content x in In x Ga1-x N, prevented by the indium segregation within the miscibility gap. Beyond the known advantage of dislocation-free growth on dissimilar substrates, nanowires may help to extend the compositional range of InGaN. However, the necessary control over the material homogeneity is still lacking. Here, we present In x Ga1-x N nanowires grown by hydride vapor phase epitaxy on silicon substrates, showing rather homogeneous compositions and emitting from blue to red. The InN fraction in nanowires is tuned from x = 0.17 up to x = 0.7 by changing the growth temperature between 630 °C and 680 °C and adjusting some additional parameters. A dedicated model is presented, which attributes the wide compositional range of nanowires to the purely kinetic growth regime of self-catalyzed InGaN nanowires without macroscopic nucleation. These results may pave a new way for the controlled synthesis of indium-rich InGaN structures for optoelectronic applications in the extended spectral range.

Dopant radial inhomogeneity in Mg-doped GaN nanowires.

Using atom probe tomography, it is demonstrated that Mg doping of GaN nanowires grown by Molecular Beam Epitaxy results in a marked radial inhomogeneity, namely a higher Mg content in the periphery of the nanowires. This spatial inhomogeneity is attributed to a preferential incorporation of Mg through the m-plane sidewalls of nanowires and is related to the formation of a Mg-rich surface which is stabilized by hydrogen. This is further supported by Raman spectroscopy experiments which give evidence of Mg-H complexes in the doped nanowires. A Mg doping mechanism such as this, specific to nanowires, may lead to higher levels of Mg doping than in layers, boosting the potential interest of nanowires for light emitting diode applications.

Thin-Wall GaN/InAlN Multiple Quantum Well Tubes.

Thin-wall tubes composed of nitride semiconductors (III-N compounds) based on GaN/InAlN multiple quantum wells (MQWs) are fabricated by metal-organic vapor-phase epitaxy in a simple and full III-N approach. The synthesis of such MQW-tubes is based on the growth of N-polar c-axis vertical GaN wires surrounded by a core-shell MQW heterostructure followed by in situ selective etching using controlled H2/NH3 annealing at 1010 °C to remove the inner GaN wire part. After this process, well-defined MQW-based tubes having nonpolar m-plane orientation exhibit UV light near 330 nm up to room temperature, consistent with the emission of GaN/InAlN MQWs. Partially etched tubes reveal a quantum-dotlike signature originating from nanosized GaN residuals present inside the tubes. The possibility to fabricate in a simple way thin-wall III-N tubes composed of an embedded MQW-based active region offering controllable optical emission properties constitutes an important step forward to develop new nitride devices such as emitters, detectors or sensors based on tubelike nanostructures.

Self-catalyzed GaAs nanowires on silicon by hydride vapor phase epitaxy.

Gold-free GaAs nanowires on silicon substrates can pave the way for monolithic integration of photonic nanodevices with silicon electronic platforms. It is extensively documented that the self-catalyzed approach works well in molecular beam epitaxy but is much more difficult to implement in vapor phase epitaxies. Here, we report the first gallium-catalyzed hydride vapor phase epitaxy growth of long (more than 10 µm) GaAs nanowires on Si(111) substrates with a high integrated growth rate up to 60 µm h-1 and pure zincblende crystal structure. The growth is achieved by combining a low temperature of 600 °C with high gaseous GaCl/As flow ratios to enable dechlorination and formation of gallium droplets. GaAs nanowires exhibit an interesting bottle-like shape with strongly tapered bases, followed by straight tops with radii as small as 5 nm. We present a model that explains the peculiar growth mechanism in which the gallium droplets nucleate and rapidly swell on the silicon surface but then are gradually consumed to reach a stationary size. Our results unravel the necessary conditions for obtaining gallium-catalyzed GaAs nanowires by vapor phase epitaxy techniques.

Composition Analysis of III-Nitrides at the Nanometer Scale: Comparison of Energy Dispersive X-ray Spectroscopy and Atom Probe Tomography.

The enhancement of the performance of advanced nitride-based optoelectronic devices requires the fine tuning of their composition, which has to be determined with a high accuracy and at the nanometer scale. For that purpose, we have evaluated and compared energy dispersive X-ray spectroscopy (EDX) in a scanning transmission electron microscope (STEM) and atom probe tomography (APT) in terms of composition analysis of AlGaN/GaN multilayers. Both techniques give comparable results with a composition accuracy better than 0.6 % even for layers as thin as 3 nm. In case of EDX, we show the relevance of correcting the X-ray absorption by simultaneous determination of the mass thickness and chemical composition at each point of the analysis. Limitations of both techniques are discussed when applied to specimens with different geometries or compositions.

Flexible Photodiodes Based on Nitride Core/Shell p-n Junction Nanowires.

A flexible nitride p-n photodiode is demonstrated. The device consists of a composite nanowire/polymer membrane transferred onto a flexible substrate. The active element for light sensing is a vertical array of core/shell p-n junction nanowires containing InGaN/GaN quantum wells grown by MOVPE. Electron/hole generation and transport in core/shell nanowires are modeled within nonequilibrium Green function formalism showing a good agreement with experimental results. Fully flexible transparent contacts based on a silver nanowire network are used for device fabrication, which allows bending the detector to a few millimeter curvature radius without damage. The detector shows a photoresponse at wavelengths shorter than 430 nm with a peak responsivity of 0.096 A/W at 370 nm under zero bias. The operation speed for a 0.3 × 0.3 cm2 detector patch was tested between 4 Hz and 2 kHz. The -3 dB cutoff was found to be ∼35 Hz, which is faster than the operation speed for typical photoconductive detectors and which is compatible with UV monitoring applications.