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.

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.

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.

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.

InGaN nanowires with high InN molar fraction: growth, structural and optical properties.

The structural and optical properties of axial GaN/InGaN/GaN nanowire heterostructures with high InN molar fractions grown by molecular beam epitaxy have been studied at the nanoscale by a combination of electron microscopy, extended x-ray absorption fine structure and nano-cathodoluminescence techniques. InN molar fractions up to 50% have been successfully incorporated without extended defects, as evidence of nanowire potentialities for practical device realisation in such a composition range. Taking advantage of the N-polarity of the self-nucleated GaN NWs grown by molecular beam epitaxy on Si(111), the N-polar InGaN stability temperature diagram has been experimentally determined and found to extend to a higher temperature than its metal-polar counterpart. Furthermore, annealing of GaN-capped InGaN NWs up to 800 °C has been found to result in a 20 times increase of photoluminescence intensity, which is assigned to point defect curing.

Flexible Light-Emitting Diodes Based on Vertical Nitride Nanowires.

We demonstrate large area fully flexible blue LEDs based on core/shell InGaN/GaN nanowires grown by MOCVD. The fabrication relies on polymer encapsulation, nanowire lift-off and contacting using silver nanowire transparent electrodes. The LEDs exhibit rectifying behavior with a light-up voltage around 3 V. The devices show no electroluminescence degradation neither under multiple bending down to 3 mm curvature radius nor in time for more than one month storage in ambient conditions without any protecting encapsulation. Fully transparent flexible LEDs with high optical transmittance are also fabricated. Finally, a two-color flexible LED emitting in the green and blue spectral ranges is demonstrated combining two layers of InGaN/GaN nanowires with different In contents.

Ultralong and defect-free GaN nanowires grown by the HVPE process.

GaN nanowires with exceptional lengths are synthesized by vapor-liquid-solid coupled with near-equilibrium hydride vapor phase epitaxy technique on c-plane sapphire substrates. Because of the high decomposition frequency of GaCl precursors and a direct supply of Ga through the catalyst particle, the growth of GaN nanowires with constant diameters takes place at an exceptional growth rate of 130 µm/h. The chemical composition of the catalyst droplet is analyzed by energy dispersive X-ray spectroscopy. High-resolution transmission electron microscopy and selective area diffraction show that the GaN nanowires crystallize in the hexagonal wurzite structure and are defect-free. GaN nanowires exhibit bare top facets without any droplet. Microphotoluminescence displays a narrow and intense emission line (1 meV line width) associated to the neutral-donor bound exciton revealing excellent optical properties of GaN nanowires.

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.

M-plane core-shell InGaN/GaN multiple-quantum-wells on GaN wires for electroluminescent devices.

Nonpolar InGaN/GaN multiple quantum wells (MQWs) grown on the {11-00} sidewalls of c-axis GaN wires have been grown by organometallic vapor phase epitaxy on c-sapphire substrates. The structural properties of single wires are studied in detail by scanning transmission electron microscopy and in a more original way by secondary ion mass spectroscopy to quantify defects, thickness (1-8 nm) and In-composition in the wells (∼16%). The core-shell MQW light emission characteristics (390-420 nm at 5 K) were investigated by cathodo- and photoluminescence demonstrating the absence of the quantum Stark effect as expected due to the nonpolar orientation. Finally, these radial nonpolar quantum wells were used in room-temperature single-wire electroluminescent devices emitting at 392 nm by exploiting sidewall 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.

Ordering of Pd(2+) and Pd(4+) in the mixed-valent palladate KPd(2)O(3).

A new potassium palladate KPd(2)O(3) was synthesized by the reaction of KO(2) and PdO at elevated oxygen pressure. Its crystal structure was solved from powder X-ray diffraction data in the space group R3m (a = 6.0730(1) A, c = 18.7770(7) A, and Z = 6). KPd(2)O(3) represents a new structure type, consisting of an alternating sequence of K(+) and Pd(2)O(3)(-) layers with ordered Pd(2+) and Pd(4+) ions. The presence of palladium ions in di- and tetravalent low-spin states was confirmed by magnetic susceptibility measurements.