Inhomogeneous spatial distribution of non radiative recombination centers in GaN/InGaN nanowire heterostructures studied by cathodoluminescence.

In order to elucidate the mechanisms responsible for cathodoluminescence intensity variations at the scale of single InGaN/GaN nanowire heterostructures, a methodology is proposed based on a statistical analysis on ensembles of several hundreds of nanowires exhibiting a diameter of 180, 240 and 280 nm. For 180 nm diameter, we find that intensitiy variations are consistent with incorporation of point defects obeying Poisson's statistics. For wider diameters, intensity variations at the scale of single NWs are observed and assigned to local growth conditions fluctuations. Finally, for the less luminescent nanowires, a departure from Poisson's statistics is observed suggesting the possible clustering of non independent point defects.

Ultrathin GaN quantum wells in AlN nanowires for UV-C emission.

Molecular beam epitaxy growth and optical properties of GaN quantum disks in AlN nanowires were investigated, with the purpose of controlling the emission wavelength of AlN nanowire-based light emitting diodes. Besides GaN quantum disks with a thickness ranging from 1 to 4 monolayers, a special attention was paid to incomplete GaN disks exhibiting lateral confinement. Their emission consists of sharp lines which extend down to 215 nm, in the vicinity of AlN band edge. The room temperature cathodoluminescence intensity of an ensemble of GaN quantum disks embedded in AlN nanowires is about 20% of the low temperature value, emphasizing the potential of ultrathin/incomplete GaN quantum disks for deep UV emission.

The role of surface states and point defects on optical properties of InGaN/GaN multi-quantum wells in nanowires grown by molecular beam epitaxy.

The optical properties of nanowire-based InGaN/GaN multiple quantum wells (MQWs) heterostructures grown by plasma-assisted molecular beam epitaxy are investigated. The beneficial effect of an InGaN underlayer grown below the active region is demonstrated and assigned to the trapping of point defects transferred from the pseudo-template to the active region. The influence of surface recombination is also investigated. For low InN molar fraction value, we demonstrate that AlOxdeposition efficiently passivate the surface. By contrast, for large InN molar fraction, the increase of volume non-radiative recombination, which we assign to the formation of additional point defects during the growth of the heterostructure dominates surface recombination. The inhomogeneous luminescence of single nanowires at the nanoscale, namely a luminescent ring surrounding a less luminescent centre part points towards an inhomogeneous spatial distribution of the non-radiative recombination center tentatively identified as intrinsic point defects created during the MQWs growth. These results can contribute to improve the performances of microLEDs in the visible range.

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.

Role of Ga Surface Diffusion in the Elongation Mechanism and Optical Properties of Catalyst-Free GaN Nanowires Grown by Molecular Beam Epitaxy.

We have shown that both the morphology and elongation mechanism of GaN nanowires homoepitaxially grown by plasma-assisted molecular beam epitaxy (PA-MBE) on a [0001]-oriented GaN nanowire template are strongly affected by the nominal gallium/nitrogen flux ratio as well as by additional Ga flux diffusing from the side walls. Nitrogen-rich growth conditions are found to be associated with a surface energy-driven morphology and reduced Ga diffusion on the (0001) plane. This leads to random nucleation on the (0001) top surface and preferential material accumulation at the periphery. By contrast, gallium-rich growth conditions are characterized by enhanced Ga surface diffusion promoting a kinetically driven morphology. This regime is governed by a potential barrier that limits diffusion from the top surface toward nanowire side walls, leading to a concave nanowire top surface morphology. Switching from one regime to the other can be achieved using the surfactant effect of an additional In flux. The optical properties are found to be strongly affected by growth mode, with point defect incorporation and stacking fault formation depending on gallium/nitrogen flux ratio.

Mg and In Codoped p-type AlN Nanowires for pn Junction Realization.

Efficient, mercury-free deep ultraviolet (DUV) light-emitting diodes (LEDs) are becoming a crucial challenge for many applications such as water purification. For decades, the poor p-type doping and difficult current injection of Al-rich AlGaN-based DUV LEDs have limited their efficiency and therefore their use. We present here the significant increase in AlN p-doping thanks to Mg/In codoping, which leads to an order of magnitude higher Mg solubility limit in AlN nanowires (NWs). Optimal electrical activation of acceptor impurities has been further achieved by electron irradiation, resulting in tunnel conduction through the AlN NW p-n junction. The proposed theoretical scenario to account for enhanced Mg incorporation involves an easy ionization of In-vacancy complex associated with a negative charging of Mg in In vicinity. This leads to favored incorporation of negatively charged Mg into the AlN matrix, opening the path to the realization of highly efficient NW-based LEDs in the DUV range.

Spontaneous intercalation of Ga and In bilayers during plasma-assisted molecular beam epitaxy growth of GaN on graphene on SiC.

The formation of a self-limited metallic bilayer is reported during the growth of GaN by plasma-assisted molecular beam epitaxy on graphene on (0001) SiC. Depending on growth conditions, this layer may consist of either Ga or In, which gets intercalated between graphene and the SiC surface. Diffusion of metal atoms is eased by steps at SiC surface and N plasma induced defects in the graphene layer. Energetically favorable wetting of the (0001) SiC surface by Ga or In is tentatively assigned to the breaking of covalent bonds between (0001) SiC surface and carbon buffer layer. As a consequence, graphene doping and local strain/doping fluctuations decrease. Furthermore, the presence of a metallic layer below GaN opens the way to the development of devices with a spontaneously formed metallic electrode on their back side.

Axial p-n junction and space charge limited current in single GaN nanowire.

The electrical characterizations of individual basic GaN nanostructures, such as axial nanowire (NW) p-n junctions, are becoming indispensable and crucial for the fully controlled realization of GaN NW based devices. In this study, electron beam induced current (EBIC) measurements were performed on two single axial GaN p-n junction NWs grown by plasma-assisted molecular beam epitaxy. I-V characteristics revealed that both ohmic and space charge limited current (SCLC) regimes occur in GaN p-n junction NW. Thanks to an improved contact process, both the electric field induced by the p-n junction and the SCLC in the p-part of GaN NW were disclosed and delineated by EBIC signals under different biases. Analyzing the EBIC profiles in the vicinity of the p-n junction under 0 V and reverse bias, we deduced a depletion width in the range of 116-125 nm. Following our previous work, the acceptor N a doping level was estimated to be 2-3 × 1017 at cm-3 assuming a donor level N d of 2-3 × 1018 at cm-3. The hole diffusion length in n-GaN was determined to be 75 nm for NW #1 and 43 nm for NW #2, demonstrating a low surface recombination velocity at the m-plane facet of n-GaN NW. Under forward bias, EBIC imaging visualized the electric field induced by the SCLC close to p-side contact, in agreement with unusual SCLC previously reported in GaN NWs.

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.

Direct assessment of p-n junctions in single GaN nanowires by Kelvin probe force microscopy.

Making use of Kelvin probe force microscopy, in dark and under ultraviolet illumination, we study the characteristics of p-n junctions formed along the axis of self-organized GaN nanowires (NWs). We map the contact potential difference of the single NW p-n junctions to locate the space charge region and directly measure the depletion width and the junction voltage. Simulations indicate a shrinkage of the built-in potential for NWs with small diameter due to surface band bending, in qualitative agreement with the measurements. The photovoltage of the NW/substrate contact is studied by analyzing the response of NW segments with p- and n-type doping under illumination. Our results show that the shifts of the Fermi levels, and not the changes in surface band bending, are the most important effects under above band-gap illumination. The quantitative electrical information obtained here is important for the use of NW p-n junctions as photovoltaic or rectifying devices at the nanoscale, and is especially relevant since the technique does not require the formation of ohmic contacts to the NW junction.

Growth mechanism of InGaN nano-umbrellas.

It is demonstrated that growing InGaN nanowires in metal-rich conditions on top of GaN nanowires results in a widening of the InGaN section. It is shown that the widening is eased by stacking faults (SFs) formation, revealing facets favorable to In incorporation. It is furthermore put in evidence that partial dislocations terminating SFs efficiently contribute to elastic strain relaxation. Indium accumulation on top of the InGaN section is found to result in an axial growth rate decrease, which has been assigned to increased N-N recombination and subsequent effective nitrogen flux decrease, eventually leading to the formation of InGaN nano-umbrellas/nanoplatelets.

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.

Si Donor Incorporation in GaN Nanowires.

With increasing interest in GaN based devices, the control and evaluation of doping are becoming more and more important. We have studied the structural and electrical properties of a series of Si-doped GaN nanowires (NWs) grown by molecular beam epitaxy (MBE) with a typical dimension of 2-3 µm in length and 20-200 nm in radius. In particular, high resolution energy dispersive X-ray spectroscopy (EDX) has illustrated a higher Si incorporation in NWs than that in two-dimensional (2D) layers and Si segregation at the edge of the NW with the highest doping. Moreover, direct transport measurements on single NWs have shown a controlled doping with resistivity from 10(2) to 10(-3) Ω·cm, and a carrier concentration from 10(17) to 10(20) cm(-3). Field effect transistor (FET) measurements combined with finite element simulation by NextNano(3) software have put in evidence the high mobility of carriers in the nonintentionally doped (NID) NWs.

Optical anisotropy and light extraction efficiency of MBE grown GaN nanowires epilayers.

The use of nanowires as active medium seems very promising for the development of high brightness LEDs. With a lower effective refractive index than bulk, semiconductor nanowire layers may lead to a high light extraction efficiency. We hereafter discuss the anisotropic properties of dense arrays of molecular beam epitaxy (MBE) grown gallium nitride (GaN) nanowires and the consequences on the optical design of nanowire based LEDs. In particular we show numerically that light extraction efficiency as high as 72% can be expected for GaN nanowires layer grown on a low cost Si substrate.

Enhanced UV Emission of GaN Nanowires Functionalized by Wider Band Gap Solution-Processed p-MnO Quantum Dots.

GaN-based UV light-emitting devices suffer from low efficiency. To mitigate this issue, we hybridized GaN nanowires (NWs) grown on Si substrates by plasma-assisted molecular beam epitaxy with solution-processed p-type MnO quantum dots (QDs) characterized by a wider band gap (∼5 eV) than that of GaN. Further investigations reveal that the photoluminescence intensity of the GaN NWs increases up to ∼3.9-fold (∼290%) after functionalizing them with p-MnO QDs, while the internal quantum efficiency is improved by ∼1.7-fold. Electron energy loss spectroscopy (EELS) incorporated into transmission electron microscopy reveals an increase in the density of states in QD-decorated NWs compared to the bare ones. The advanced optical and EELS analyses indicate that the energy transfer from the wider band gap p-MnO QDs to n-GaN NW can lead to substantial emission enhancement and greater radiative recombination contribution because of the good band alignment between MnO QDs and GaN NWs. This work provides valuable insights into an environmentally friendly strategy for improving UV device performance.

Direct Measurement of Polarization-Induced Fields in GaN/AlN by Nano-Beam Electron Diffraction.

The built-in piezoelectric fields in group III-nitrides can act as road blocks on the way to maximizing the efficiency of opto-electronic devices. In order to overcome this limitation, a proper characterization of these fields is necessary. In this work nano-beam electron diffraction in scanning transmission electron microscopy mode has been used to simultaneously measure the strain state and the induced piezoelectric fields in a GaN/AlN multiple quantum well system.

Effect of Eu-implantation and annealing on the GaN quantum dots excitonic recombination.

Undoped self-assembled GaN quantum dots (QD) stacked in superlattices (SL) with AlN spacer layers were submitted to thermal annealing treatments. Changes in the balance between the quantum confinement, strain state of the stacked heterostructures and quantum confined Stark effect lead to the observation of GaN QD excitonic recombination above and below the bulk GaN bandgap. In Eu-implanted SL structures, the GaN QD recombination was found to be dependent on the implantation fluence. For samples implanted with high fluence, a broad emission band at 2.7 eV was tentatively assigned to the emission of large blurred GaN QD present in the damage region of the implanted SL. This emission band is absent in the SL structures implanted with lower fluence and hence lower defect level. In both cases, high energy emission bands at approx. 3.9 eV suggest the presence of smaller dots for which the photoluminescence intensity was seen to be constant with increasing temperatures. Despite the fact that different deexcitation processes occur in undoped and Eu-implanted SL structures, the excitation population mechanisms were seen to be sample-independent. Two main absorption bands with maxima at approx. 4.1 and 4.7 to 4.9 eV are responsible for the population of the optically active centres in the SL samples.

Exciton and biexciton luminescence from single GaN/AlN quantum dots in nanowires.

We present a microphotoluminescence study of single GaN/AlN quantum dots embedded in single nanowires. At low excitation power, single exciton lines with full width at half-maximum as narrow as 1 meV are observed. The study of the excitation power dependence of the emission allows us to identify the biexciton transitions with binding energies ranging from 20 to 40 meV.