Deep-Level Structure of the Spin-Active Recombination Center in Dilute Nitrides.

A gallium interstitial defect is thought to be responsible for the spectacular spin-dependent recombination in GaAs_{1-x}N_{x} dilute nitrides. Current understanding associates this defect with at least two in-gap levels corresponding to the (+/0) and (++/+) charge-state transitions. Using a spin-sensitive photoinduced current transient spectroscopy, the in-gap electronic structure of a x=0.021 alloy is revealed. The (+/0) state lies ≈0.27 eV below the conduction band edge, and an anomalous, negative activation energy reveals the presence of not one but two other in-gap states. The observations are consistent with a (++/+) state ≈0.19 eV above the valence band edge, and a (+++/++) state ≈25 meV above the valence band edge.

Correlated optical and structural analyses of individual GaAsP/GaP core-shell nanowires.

We report on the structural and optical properties of GaAs0.7P0.3/GaP core-shell nanowires (NWs) for future photovoltaic applications. The NWs are grown by self-catalyzed molecular beam epitaxy. Scanning transmission electron microscopy (STEM) analyses demonstrate that the GaAsP NW core develops an inverse-tapered shape with a formation of an unintentional GaAsP shell having a lower P content. Without surface passivation, this unintentional shell produces no luminescence because of strong surface recombination. However, passivation of the surface with a GaP shell leads to the appearance of a secondary peak in the luminescence spectrum arising from this unintentional shell. The attribution of the luminescence peaks is confirmed by correlated cathodoluminescence and STEM analyses of the same NW.

Optical properties of GaN nanowires grown on chemical vapor deposited-graphene.

Optical properties of GaN nanowires (NWs) grown on chemical vapor deposited-graphene transferred on an amorphous support are reported. The growth temperature was optimized to achieve a high NW density with a perfect selectivity with respect to a SiO2 surface. The growth temperature window was found to be rather narrow (815°C ± 5°C). Steady-state and time-resolved photoluminescence from GaN NWs grown on graphene was compared with the results for GaN NWs grown on conventional substrates within the same molecular beam epitaxy reactor showing a comparable optical quality for different substrates. Growth at temperatures above 820 °C led to a strong NW density reduction accompanied with a diameter narrowing. This morphology change leads to a spectral blueshift of the donor-bound exciton emission line due to either surface stress or dielectric confinement. Graphene multi-layered micro-domains were explored as a way to arrange GaN NWs in a hollow hexagonal pattern. The NWs grown on these domains show a luminescence spectral linewidth as low as 0.28 meV (close to the set-up resolution limit).

In situ passivation of GaAsP nanowires.

We report on the structural and optical properties of GaAsP nanowires (NWs) grown by molecular-beam epitaxy. By adjusting the alloy composition in the NWs, the transition energy was tuned to the optimal value required for tandem III-V/silicon solar cells. We discovered that an unintentional shell was also formed during the GaAsP NW growth. The NW surface was passivated by an in situ deposition of a radial Ga(As)P shell. Different shell compositions and thicknesses were investigated. We demonstrate that the optimal passivation conditions for GaAsP NWs (with a gap of 1.78 eV) are obtained with a 5 nm thick GaP shell. This passivation enhances the luminescence intensity of the NWs by 2 orders of magnitude and yields a longer luminescence decay. The luminescence dynamics changes from single exponential decay with a 4 ps characteristic time in non-passivated NWs to a bi-exponential decay with characteristic times of 85 and 540 ps in NWs with GaP shell passivation.

Piezo-generator integrating a vertical array of GaN nanowires.

We demonstrate the first piezo-generator integrating a vertical array of GaN nanowires (NWs). We perform a systematic multi-scale analysis, going from single wire properties to macroscopic device fabrication and characterization, which allows us to establish for GaN NWs the relationship between the material properties and the piezo-generation, and to propose an efficient piezo-generator design. The piezo-conversion of individual MBE-grown p-doped GaN NWs in a dense array is assessed by atomic force microscopy (AFM) equipped with a Resiscope module yielding an average output voltage of 228 ± 120 mV and a maximum value of 350 mV generated per NW. In the case of p-doped GaN NWs, the piezo-generation is achieved when a positive piezo-potential is created inside the nanostructures, i.e. when the NWs are submitted to compressive deformation. The understanding of the piezo-generation mechanism in our GaN NWs, gained from AFM analyses, is applied to design a piezo-generator operated under compressive strain. The device consists of NW arrays of several square millimeters in size embedded into spin-on glass with a Schottky contact for rectification and collection of piezo-generated carriers. The generator delivers a maximum power density of ∼12.7 mW cm(-3). This value sets the new state of the art for piezo-generators based on GaN NWs and more generally on nitride NWs, and offers promising prospects for the use of GaN NWs as high-efficiency ultra-compact energy harvesters.

Self-induced growth of vertical GaN nanowires on silica.

We study the self-induced growth of GaN nanowires on silica. Although the amorphous structure of this substrate offers no possibility of an epitaxial relationship, the nanowires are remarkably aligned with the substrate normal whereas, as expected, their in-plane orientation is random. Their structural and optical characteristics are compared to those of GaN nanowires grown on standard crystalline Si (111) substrates. The polarity inversion domains are much less frequent, if not totally absent, in the nanowires grown on silica, which we find to be N-polar. This work demonstrates that high-quality vertical GaN nanowires can be elaborated without resorting to bulk crystalline substrates.

New mode of vapor-liquid-solid nanowire growth.

We report on the new mode of the vapor-liquid-solid nanowire growth with a droplet wetting the sidewalls and surrounding the nanowire rather than resting on its top. It is shown theoretically that such an unusual configuration happens when the growth is catalyzed by a lower surface energy metal. A model of a nonspherical elongated droplet shape in the wetting case is developed. Theoretical predictions are compared to the experimental data on the Ga-catalyzed growth of GaAs nanowires by molecular beam epitaxy. In particular, it is demonstrated that the experimentally observed droplet shape is indeed nonspherical. The new VLS mode has a major impact on the crystal structure of GaAs nanowires, helping to avoid the uncontrolled zinc blende-wurtzite polytylism under optimized growth conditions. Since the triple phase line nucleation is suppressed on surface energetic grounds, all nanowires acquire pure zinc blende phase along the entire length, as demonstrated by the structural studies of our GaAs nanowires.

Morphology of self-catalyzed GaN nanowires and chronology of their formation by molecular beam epitaxy.

GaN nanowires are synthesized by plasma-assisted molecular beam epitaxy on Si(111) substrates. The strong impact of the cell orientation relative to the substrate on the nanowire morphology is shown. To study the kinetics of growth, thin AlN markers are introduced periodically during NW growth. These markers are observed in single nanowires by transmission electron microscopy, giving access to the chronology of the nanowire formation and to the time evolution of the nanowire morphology. A long delay precedes the beginning of nanowire formation. Then, their elongation proceeds at a constant rate. Later, shells develop on the side-wall facets by ascending growth of layer bunches which first agglomerate at the nanowire foot.

Crystal phase quantum dots.

In semiconducting nanowires, both zinc blende and wurtzite crystal structures can coexist. The band structure difference between the two structures can lead to charge confinement. Here we fabricate and study single quantum dot devices defined solely by crystal phase in a chemically homogeneous nanowire and observe single photon generation. More generally, our results show that this type of carrier confinement represents a novel degree of freedom in device design at the nanoscale.

Room-temperature defect-engineered spin filter based on a non-magnetic semiconductor.

Generating, manipulating and detecting electron spin polarization and coherence at room temperature is at the heart of future spintronics and spin-based quantum information technology. Spin filtering, which is a key issue for spintronic applications, has been demonstrated by using ferromagnetic metals, diluted magnetic semiconductors, quantum point contacts, quantum dots, carbon nanotubes, multiferroics and so on. This filtering effect was so far restricted to a limited efficiency and primarily at low temperatures or under a magnetic field. Here, we provide direct and unambiguous experimental proof that an electron-spin-polarized defect, such as a Ga(i) self-interstitial in dilute nitride GaNAs, can effectively deplete conduction electrons with an opposite spin orientation and can thus turn the non-magnetic semiconductor into an efficient spin filter operating at room temperature and zero magnetic field. This work shows the potential of such defect-engineered, switchable spin filters as an attractive alternative to generate, amplify and detect electron spin polarization at room temperature without a magnetic material or external magnetic fields.

Wurtzite GaAs/AlGaAs core-shell nanowires grown by molecular beam epitaxy.

We report the growth of GaAs/AlGaAs core-shell nanowires (NWs) on GaAs(111)B substrates by Au-assisted molecular beam epitaxy. Electron microscopy shows the formation of a wurtzite AlGaAs shell structure both in the radial and the axial directions outside a wurtzite GaAs core. With higher Al content, a lower axial and a higher radial growth rate of the AlGaAs shell were observed. Room temperature and low temperature (4.4 K) micro-photoluminescence measurements show a much higher radiative efficiency from the GaAs core after the NW is overgrown with a radial AlGaAs shell.

Electron spin control in dilute nitride semiconductors.

We report on a study of spin-dependent recombination processes (SDR) for conduction band electrons on deep paramagnetic centers in a series of GaAs(1-y)N(y) epilayers by time-resolved optical orientation experiments. We demonstrate that this dilute nitride compound can be used as an effective electron spin filter under a polarized optical excitation of appropriate intensity. This optimum intensity can moreover be controlled by adjusting the nitrogen composition in the layer.

Femtosecond pulse generation around 1500 nm using a GaInNAsSb SESAM.

The operation of a femtosecond Cr(4+):YAG laser that incorporates a novel GaInNAsSb semiconductor saturable Bragg reflector is reported. In the mode-locked regime 230 fs pulses centred at 1528 nm were generated at an average output power of 280 mW. The SESAM exhibited a low saturation fluence of 10 microJ/cm(2) and a short recovery time of 12 ps.

Shape modification of III-V nanowires: the role of nucleation on sidewalls.

The effect of sidewall nucleation on nanowire morphology is studied theoretically. The model provides a semiquantitative description of nanowire radius as a function of its length and the distance from the surface. It is demonstrated that the wire shape critically depends on the diffusion flux of adatoms from the substrate and on the rate of direct impingement to the sidewalls. At high diffusion flux the wire shape is cylindrical. A decrease of diffusion from the surface leads to the onset of nucleation on the sidewalls resulting in the lateral extension and in the reduction of wire length. The wire shape changes from cylindrical to conical, because the supersaturation of adatoms driving the nucleation is higher at the wire foot than at the top. It is shown that the shape modification becomes pronounced at low growth temperatures. Theoretical results are used to model the experimentally observed shapes of GaAs and GaP wires, grown by Au-assisted molecular beam epitaxy at different temperatures.

Theoretical analysis of the vapor-liquid-solid mechanism of nanowire growth during molecular beam epitaxy.

A theoretical model of nanowire formation by the vapor-liquid-solid mechanism during molecular beam epitaxy and related growth techniques is presented. The model unifies the conventional adsorption-induced model, the diffusion-induced model, and the model of nucleation-mediated growth on the liquid-solid interface. The concentration of deposit atoms in the liquid alloy, the nanowire diameter, and all other characteristics of the growth process are treated dynamically as functions of the growth time. The model provides theoretical length-diameter dependences of nanowires and the dependence of the nanowire length on the technologically controlled growth conditions, such as the surface temperature and the deposition thickness. In particular, it is shown that the length-diameter curves of nanowires might convert from decreasing to increasing at a certain critical diameter and that the nanowires taper when their length becomes comparable with the adatom diffusion length on the sidewalls. The theoretical dependence of the nanowire morphology on its lateral size and length and on the surface temperature are compared to the available experimental data obtained recently for Si and nanowires.

Effects of temperature on transition energies of GaAsSbN/GaAs single quantum wells.

The energy transitions of GaAsSbN/GaAs strained-layer single quantum wells (QWs), grown by molecular-beam epitaxy, are studied in detail, using photoluminescence (PL) and photoreflectance (PR) spectroscopies. The optical transitions energy observed in the PL and PR spectra of GaAsSbN/GaAs QWs show a strong decrease with a small increase in the N composition. These effects are explained through the interaction between the conduction band and a narrow resonant band formed by nitrogen states in the GaAsSbN alloy. The temperature dependence of ground-state energy of strained-layer QWs is analyzed using the Bose-Einstein relation in the temperature range from 9 to 295 K. The parameters that describe the temperature variations of the ground-state energies are evaluated and discussed.

Growth of Inclined GaAs Nanowires by Molecular Beam Epitaxy: Theory and Experiment.

The growth of inclined GaAs nanowires (NWs) during molecular beam epitaxy (MBE) on the rotating substrates is studied. The growth model provides explicitly the NW length as a function of radius, supersaturations, diffusion lengths and the tilt angle. Growth experiments are carried out on the GaAs(211)A and GaAs(111)B substrates. It is found that 20° inclined NWs are two times longer in average, which is explained by a larger impingement rate on their sidewalls. We find that the effective diffusion length at 550°C amounts to 12 nm for the surface adatoms and is more than 5,000 nm for the sidewall adatoms. Supersaturations of surface and sidewall adatoms are also estimated. The obtained results show the importance of sidewall adatoms in the MBE growth of NWs, neglected in a number of earlier studies.

Facet and in-plane crystallographic orientations of GaN nanowires grown on Si(111).

We have determined the in-plane orientation of GaN nanowires relative to the Si (111) substrate on which they were grown. We used x-ray diffraction pole figure measurements to evidence two types of crystallographic orientation, all the nanowires having [Formula: see text] lateral facets. The proportion of these two orientations was determined and shown to be influenced by the pre-deposition of Al(Ga)N intermediate layers. In the main orientation, the GaN basal [Formula: see text] directions are aligned with the [Formula: see text] directions. This orientation corresponds to an in-plane coincidence of GaN and Si lattices.

Zinc blende GaAsSb nanowires grown by molecular beam epitaxy.

We report the growth of GaAsSb nanowires (NWs) on GaAs(111)B substrates by Au-assisted molecular beam epitaxy. The structural characteristics of the GaAsSb NWs have been investigated in detail. Their Sb mole fraction was found to be about 25%. Their crystal structure was found to be pure zinc blende (ZB), in contrast to the wurtzite structure observed in GaAs NWs grown under similar conditions. The ZB GaAsSb NWs exhibit rotational twins around their [111]B growth axis, with twin-free segments as long as 500 nm. The total volumes of GaAsSb segments with twinned and un-twinned orientations, respectively, were found to be equal by x-ray diffraction analysis of NW ensembles.

Temperature conditions for GaAs nanowire formation by Au-assisted molecular beam epitaxy.

Molecular beam epitaxial growth of GaAs nanowires using Au particles as a catalyst was investigated. Prior to the growth during annealing, Au alloyed with Ga coming from the GaAs substrate, and melted. Phase transitions of the resulting particles were observed in situ by reflection high-energy electron diffraction (RHEED). The temperature domain in which GaAs nanowire growth is possible was determined. The lower limit of this domain (320 °C) is close to the observed catalyst solidification temperature. Below this temperature, the catalyst is buried by GaAs growth. Above the higher limit (620 °C), the catalyst segregates on the surface with no significant nanowire formation. Inside this domain, the influence of growth temperature on the nanowire morphology and crystalline structure was investigated in detail by scanning electron microscopy and transmission electron microscopy. The correlation of the nanowire morphology with the RHEED patterns observed during the growth was established. Wurtzite GaAs was found to be the dominant crystal structure of the wires.