Nanoporous GaN by selective area sublimation through an epitaxial nanomask: AlN versus SixNy.

Nanoporous GaN layers were fabricated using selective area sublimation through a self-organized AlN nanomask in a molecular beam epitaxy reactor. The obtained pore morphology, density and size were measured using plan-view and cross-section scanning electron microscopy experiments. It was found that the porosity of the GaN layers could be adjusted from 0.04 to 0.9 by changing the AlN nanomask thickness and sublimation conditions. The room temperature photoluminescence properties as a function of the porosity were analysed. In particular, a strong improvement (>100) of the room temperature photoluminescence intensity was observed for porous GaN layers with a porosity in the 0.4-0.65 range. The characteristics of these porous layers were compared to those obtained with a SixNynanomask. Furthermore, the regrowth of p-type GaN on light emitting diode structures made porous by using either an AlN or a SixNynanomask were compared.

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

We report on the growth, structural, and optical properties of GaAs/GaAsPBi core-shell nanowires (NWs) synthesized by molecular beam epitaxy (MBE). The structure presents advantageous optical properties, in particular, for near- and mid-infrared optical applications. Scanning electron microscopy shows that although the stems of GaAs/GaAsP and GaAs/GaAsBi core-shell NWs preserve the hexagonal prism shape, the GaAs/GaAsPBi core-shell NWs develop a quasi-three-fold orientational symmetry affected by the hexagonal prismatic core. Detailed structural analyses of a GaAs/GaAsPBi core-shell stem show that it crystallized with zincblende structure with a nominal shell composition of GaAs0.617P0.362Bi0.021. Photoluminescence of GaAs/GaAsPBi core-shell NWs shows the luminescent peak at 1.02 eV with high internal quantum efficiency at room temperature (IQERT∼ 6%) superior to those of MBE-grown GaAs core NWs and GaAsPBi multiple quantum wells earlier reported. Energy-dispersive x-ray spectroscopy performed on the GaAs/GaAsPBi core-shell NWs yields an estimated bandgap different from the optically measured value. We attribute this discrepancy to the NW compositional fluctuations that also may explain the high IQERT.

Correlated optical and electrical analyses of inhomogeneous core/shell InGaN/GaN nanowire light emitting diodes.

The performance of core-shell InGaN/GaN nanowire (NW) light emitting diodes (LEDs) can be limited by wire-to-wire electrical inhomogeneities. Here we investigate an array of core-shell InGaN/GaN NWs which are morphologically identical, but present electrical dissimilarities in order to understand how the nanoscale phenomena observed in individual NWs affect the working performance of the whole array. The LED shows a low number of NWs (∼20%) producing electroluminescence under operating conditions. This is related to a presence of a potential barrier at the interface between the NW core and the radially grown n-doped layer, which differently affects the electrical properties of the NWs although they are morphologically identical. The impact of the potential barrier on the performance of the NW array is investigated by correlating multi-scanning techniques, namely electron beam induced current microscopy, electroluminescence mapping and cathodoluminescence analysis. It is found that the main cause of inhomogeneity in the array is related to a non-optimized charge injection into the active region, which can be overcome by changing the contact architecture so that the electrons become injected directly in the n-doped underlayer. The LED with so-called 'front-n-contacting' is developed leading to an increase of the yield of emitting NWs from 20% to 65%.

Fabrication and electrical study of large area free-standing membrane with embedded GaP NWs for flexible devices.

Flexible optoelectronic structures are required in a wide range of applications. Large scale modified silicone-embedded n-GaP nanowire arrays of a record 6 µm thin membranes were studied. A homogeneous silicone encapsulation was enabled by G-coating using a heavy-load centrifuge. The synthesized graft-copolymers of polydimethylsiloxane (PDMS) and polystyrene demonstrated two times lower adhesion to Si compared to standard PDMS, allowing 3 square inch area high quality silicone/nanowire membrane mechanical release, preserving the growth Si substrate for a further re-use after chemical cleaning. The 90% transparent single-walled carbon nanotubes electrical contacts to the embedded n-GaP nanowires demonstrated mechanical and electrical stability. The presented methods can be used for the fabrication of large scale flexible inorganic optoelectronic devices.

Hydrogen passivation of the n-GaN nanowire/p-Si heterointerface.

The influence of hydrogen plasma treatment on the electrical and optical properties of vertical GaN nanowire (NW)/Si heterostructures synthesized via plasma assisted molecular beam epitaxy is studied. The effect of the treatment is thoroughly studied via variation of the passivation duration. Photoluminescence investigation demonstrates that the passivation affects the doping of the GaN NWs. The samples were processed as photodiodes with a top transparent electrode to obtain detailed information about the n-GaN NWs/p-Si heterointerface under illumination. The electron beam induced current measurements demonstrated the absence of potential barriers between the active parts of the diode and the contacts, indicating ohmic behavior of the latter. I-V characteristics obtained in the dark and under illumination show that hydrogen can effectively passivate the recombination centers at the GaN NWs/Si heterointerface. The optimum passivation duration, providing improved electrical properties, is found to be 10 min within the studied passivation regimes. It is demonstrated that longer treatment causes degradation of the electrical properties. The discovered phenomenon is discussed in detail.

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).

Growth optimization and characterization of regular arrays of GaAs/AlGaAs core/shell nanowires for tandem solar cells on silicon.

With a band gap value of 1.7 eV, Al0.2Ga0.8As is one of the ideal III-V alloys for the development of nanowire-based Tandem Solar Cells on silicon. Nevertheless, growing self-catalysed AlGaAs nanowires on silicon by solid-source molecular beam epitaxy is a very difficult task due to the oxidation of Al adatoms by the SiO2 layer present on the surface. Here we propose a nanowire structure including a p.i.n radial junction inside an Al0.2Ga0.8As shell grown on a p-GaAs core. The crystalline structure of such self-catalysed nanowires grown on an epi-ready Si(111) substrate (with a thin native SiO2 layer) was investigated by transmission electronic microscopy and photoluminescence. I(V) measurements performed on single nanowires have shown a diode-like behaviour corresponding to the radial p.i.n junction inside the Al0.2Ga0.8As shell. Moreover, a current generation under the electron beam was evidenced over the entire radial junction along the nanowires by means of electron beam induced current (EBIC) microscopy. The same structure was reproduced on patterned substrates with a SiO2 mask, producing an ordered hexagonal array. High and uniform yields from 83% to 87% of vertical nanowires were obtained on 0.9 × 0.9 cm2 patterned areas. EBIC mapping performed on these nanowires confirmed the good electrical properties of the radial junction within the nanowires.

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.

Excitonic Diffusion in InGaN/GaN Core-Shell Nanowires.

We report on the direct observation of the diffusion of carriers in graded InGaN/GaN quantum wells in a nanowire. By probing the local dynamics at the nanoscale, along the wire for different temperatures between 4 and 250 K, we conclude that this diffusion process is thermally activated. In addition, the analysis of the cathodoluminescence lifetime for different temperatures shows that the carrier motion is isotropic and does not follow the indium gradient. Our observations are interpreted in terms of a hopping process between localized states. We find that the random alloy fluctuations prevent any directional drift of excitons along the In gradient and therefore any carrier accumulation. Our results therefore confirm the potential of core-shell nanowires for lighting devices. Indeed, the short lifetime of m-plane quantum wells together with their large active area and the homogeneous distribution of carrier along the quantum well will decrease influence of any high carrier density effect on the efficiency of these light-emitting diodes.

Investigation of Photovoltaic Properties of Single Core-Shell GaN/InGaN Wires.

We report the investigation of the photovoltaic properties of core-shell GaN/InGaN wires. The radial structure is grown on m-plane {11̅00} facets of self-assembled c̅-axis GaN wires elaborated by metal-organic vapor phase epitaxy (MOVPE) on sapphire substrates. The conversion efficiency of wires with radial shell composed of thick In0.1Ga0.9N layers and of 30× In0.18Ga0.82N/GaN quantum wells are compared. We also investigate the impact of the contact nature and layout on the carrier collection and photovoltaic performances. The contact optimization results in an improved conversion efficiency of 0.33% and a fill factor of 83% under 1 sun (AM1.5G) on single wires with a quantum well-based active region. Photocurrent spectroscopy demonstrates that the response ascribed to the absorption of InGaN/GaN quantum wells appears at wavelengths shorter than 440 nm.

Core-shell InGaN/GaN nanowire light emitting diodes analyzed by electron beam induced current microscopy and cathodoluminescence mapping.

We report on the electron beam induced current (EBIC) microscopy and cathodoluminescence (CL) characterization correlated with compositional analysis of light emitting diodes based on core/shell InGaN/GaN nanowire arrays. The EBIC mapping of cleaved fully operational devices allows to probe the electrical properties of the active region with a nanoscale resolution. In particular, the electrical activity of the p-n junction on the m-planes and on the semi-polar planes of individual nanowires is assessed in top view and cross-sectional geometries. The EBIC maps combined with CL characterization demonstrate the impact of the compositional gradients along the wire axis on the electrical and optical signals: the reduction of the EBIC signal toward the nanowire top is accompanied by an increase of the CL intensity. This effect is interpreted as a consequence of the In and Al gradients in the quantum well and in the electron blocking layer, which influence the carrier extraction efficiency. The interface between the nanowire core and the radially grown layer is shown to produce in some cases a transitory EBIC signal. This observation is explained by the presence of charged traps at this interface, which can be saturated by electron irradiation.

Contact properties to CVD-graphene on GaAs substrates for optoelectronic applications.

The optimization of contacts between graphene and metals is important for many optoelectronic applications. In this work, we evaluate the contact resistance and sheet resistance of monolayer and few-layered graphene with different metallizations using the transfer length method (TLM). Graphene was obtained by the chemical vapor deposition technique (CVD-graphene) and transferred onto GaAs and Si/SiO2 substrates. To account for the quality of large-area contacts used in a number of practical applications, a millimeter-wide TLM pattern was used for transport measurements. Different metals--namely, Ag, Pt, Cr, Au, Ni, and Ti--have been tested. The minimal contact resistance Rc obtained in this work is 11.3 kΩ µm for monolayer CVD-graphene, and 6.3 kΩ µm for a few-layered graphene. Annealing allows us to decrease the contact resistance Rc and achieve 1.7 kΩm µm for few-layered graphene on GaAs substrate with Au contacts. The minimal sheet resistance Rsh of few-layered graphene transferred to GaAs and Si/SiO2 substrates are 0.28 kΩ/□ and 0.27 kΩ/□. The Rsh value of monolayer graphene on the GaAs substrate is 8 times higher (2.3 kΩ/□), but it reduces for the monolayer graphene on Si/SiO2 (1.4 kΩ/□). For distances between the contacts below 5 µm, a considerable reduction in the resistance per unit length was observed, which is explained by the changes in doping level caused by graphene suspension at small distances between contact pads.

Experimental and theoretical analysis of transport properties of core-shell wire light emitting diodes probed by electron beam induced current microscopy.

We report a systematic experimental and theoretical investigation of core-shell InGaN/GaN single wire light-emitting diodes (LEDs) using electron beam induced current (EBIC) microscopy. The wires were grown by catalyst-free MOVPE and processed into single wire LEDs using electron beam lithography on dispersed wires. The influence of the acceleration voltage and of the applied bias on the EBIC maps was investigated. We show that the EBIC maps provide information both on the minority carrier effects (i.e. on the local p-n junction collection efficiency) and on the majority carrier effects (i.e. the transport efficiency from the excited region toward the contacts). Because of a finite core and shell resistance a non-negligible current redistribution into the p-n junction takes place during the majority carrier transport. A theoretical model for transport in a core-shell wire is developed, allowing to explain the dependence of the EBIC profiles on the experimental parameters (the electron beam acceleration voltage and the bias applied on the device) and on the structural parameters of the wire (core and shell resistance, shunt resistance, etc). Comparison between simulated and experimental profiles provides valuable information concerning the structure inhomogeneities and gives insight into the wire electrical parameters.

Integrated photonic platform based on InGaN/GaN nanowire emitters and detectors.

We report the fabrication of a photonic platform consisting of single wire light-emitting diodes (LED) and photodetectors optically coupled by waveguides. MOVPE-grown (metal-organic vapor-phase epitaxy) InGaN/GaN p-n junction core-shell nanowires have been used for device fabrication. To achieve a good spectral matching between the emission wavelength and the detection range, different active regions containing either five narrow InGaN/GaN quantum wells or one wide InGaN segment were employed for the LED and the detector, respectively. The communication wavelength is ∼400 nm. The devices are realized by means of electron beam lithography on Si/SiO2 templates and connected by ∼100 µm long nonrectilinear SiN waveguides. The photodetector current trace shows signal variation correlated with the LED on/off switching with a fast transition time below 0.5 s.

InGaN/GaN core-shell single nanowire light emitting diodes with graphene-based p-contact.

We report on the demonstration of MOVPE-grown single nanowire InGaN/GaN core-shell light emitting diodes (LEDs) with a transparent graphene contact for hole injection. The electrical homogeneity of the graphene-contacted LED has been assessed by electron beam induced current microscopy. By comparing graphene-contacted and metal-contacted nanowire LEDs, we show that the contact layout determines the electroluminescence spectrum. The electroluminescence changes color from green to blue with increasing injection current. High-resolution cathodoluminescence on cleaved nanowires allows the location with high precision of the origin of different emitted wavelengths and demonstrates that the blue peak originates from the emission of the radial quantum well on the m-planes, whereas the green peak arises from the In-rich region at the junction between the m-planes and the semipolar planes. The spectral behavior of the electroluminescence is understood by modeling the current distribution within the nanowire.

Experimental demonstration and observation of a plasmon wave occuring at a GaAs-Au-GaN interface.

Integration of surface plasmon structures using semiconductor materials is limited due to the difficulties encountered in maintaining the resonance conditions upon packaging. We propose here a technology process allowing us to bond two semiconductors, such as gallium nitride (GaN) and gallium arsenide (GaAs), through a thin metal layer. This solution allows the excitation of a surface plasmon wave in an integrated classical Kretschmann configuration. The Letter presents various metal bonding conditions employed for Au deposited on both GaN/sapphire and GaAs substrates aiming at semiconductor-metal-semiconductor interfaces transparent at telecom wavelengths. The process conditions for the bondings are optimized using Ti/Au (3 nm/30 nm) layers on each of the wafers to be bonded under an applied pressure of 500 mbar at a low temperature of 250°C.

Optical properties of GaN-based nanowires containing a single Al(0.14)Ga(0.86)N/GaN quantum disc.

The optical properties of wurtzite GaN nanowires containing single Al0.14Ga0.86N/GaN quantum discs of different thickness have been investigated. The dependence of the photoluminescence (PL) transition energy on the quantum disc thickness and the thickness of a lateral AlGaN shell has been simulated in the framework of a three-dimensional effective mass model, accounting for the presence of a lateral AlGaN shell, strain state and the piezoelectric and spontaneous polarization. The predicted transition energies are in good agreement with the statistics realized on more than 40 single nanowire emission spectra and PL spectra of ensembles of nanowires. The emission spectra of the single quantum discs exhibit a Lorentzian shape with a homogeneous line width as low as 3 meV. Finally, we discuss the dependence of the interband transition energy on diameter.