On-Chip Electrostatic Actuation of a Photonic Wire Antenna Embedding Quantum Dots.

A photonic wire antenna embedding individual quantum dots (QDs) constitutes a promising platform for both quantum photonics and hybrid nanomechanics. We demonstrate here an integrated device in which on-chip electrodes can apply a static or oscillating bending force to the upper part of the wire. In the static regime, we achieve control over the bending direction and apply at will tensile or compressive mechanical stress on any QD. This results in a blue shift or red shift of their emission, with direct application to the realization of broadly tunable sources of quantum light. As a first illustration of operation in the dynamic regime, we excite the wire fundamental flexural mode and use the QD emission to detect the mechanical vibration. With an estimated operation bandwidth in the GHz range, electrostatic actuation opens appealing perspectives for the exploration of QD-nanowire hybrid mechanics with high-frequency vibrational modes.

Modulating the growth of chemically deposited ZnO nanowires and the formation of nitrogen- and hydrogen-related defects using pH adjustment.

ZnO nanowires (NWs) grown by chemical bath deposition (CBD) have received great interest for nanoscale engineering devices, but their formation in aqueous solution containing many impurities needs to be carefully addressed. In particular, the pH of the CBD solution and its effect on the formation mechanisms of ZnO NWs and of nitrogen- and hydrogen-related defects in their center are still unexplored. By adjusting its value in a low- and high-pH region, we show the latent evolution of the morphological and optical properties of ZnO NWs, as well as the modulated incorporation of nitrogen- and hydrogen-related defects in their center using Raman and cathodoluminescence spectroscopy. The increase in pH is related to the increase in the oxygen chemical potential (µ O), for which the formation energy of hydrogen in bond-centered sites (HBC) and VZn-NO-H defect complexes is found to be unchanged, whereas the formation energy of zinc vacancy (VZn) and zinc vacancy-hydrogen (VZn-nH) complexes steadily decreases as shown from density-functional theory calculations. Revealing that these VZn-related defects are energetically favorable to form as µ O is increased, ZnO NWs grown in the high-pH region are found to exhibit a higher density of VZn-nH defect complexes than ZnO NWs grown in the low-pH region. Annealing at 450 °C under an oxygen atmosphere helps tuning the optical properties of ZnO NWs by reducing the density of HBC and VZn-related defects, while activating the formation of VZn-NO-H defect complexes. These findings show the influence of pH on the nature of Zn(ii) species, the electrostatic interactions between these species and ZnO NW surfaces, and the formation energy of the involved defects. They emphasize the crucial role of the pH of the CBD solution and open new possibilities for simultaneously engineering the morphology of ZnO NWs and the formation of nitrogen- and hydrogen-related defects.

Optimization of the Sb2S3 Shell Thickness in ZnO Nanowire-Based Extremely Thin Absorber Solar Cells.

Extremely thin absorber (ETA) solar cells made of ZnO/TiO2/Sb2S3 core-shell nanowire heterostructures, using P3HT as the hole-transporting material (HTM), are of high interest to surpass solar cell efficiencies of their planar counterpart at lower material cost. However, no dimensional optimization has been addressed in detail, as it raises material and technological critical issues. In this study, the thickness of the Sb2S3 shell grown by chemical spray pyrolysis is tuned from a couple of nanometers to several tens of nanometers, while switching from a partially to a fully crystallized shell. The Sb2S3 shell is highly pure, and the unwanted Sb2O3 phase was not formed. The low end of the thickness is limited by challenges in the crystallization of the Sb2S3 shell, as it is amorphous at nanoscale dimensions, resulting in the low optical absorption of visible photons. In contrast, the high end of the thickness is limited by the increased density of defects in the bulk of the Sb2S3 shell, degrading charge carrier dynamics, and by the incomplete immersion of the P3HT in the structure, resulting in the poor hole collection. The best ETA solar cell with a short-circuit current density of 12.1 mA/cm2, an open-circuit voltage of 502 mV, and a photovoltaic conversion efficiency of 2.83% is obtained for an intermediate thickness of the Sb2S3 shell. These findings highlight that the incorporation of both the absorber shell and HTM in the core-shell heterostructures relies on the spacing between individual nanowires. They further elaborate the intricate nature of the dimensional optimization of an ETA cell, as it requires a fine-balanced holistic approach to correlate all the dimensions of all the components in the heterostructures.

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.

Nanoscale Dopant Profiling of Individual Semiconductor Wires by Capacitance-Voltage Measurement.

Developing nanoscale electrical characterization techniques adapted to three-dimensional (3D) geometry is essential for optimization of the epitaxial structure and doping process of nano- and microwires. In this paper, we demonstrate the assessment of the depletion width as well as the doping profile at the nanoscale of individual microwire core-shell light-emitting devices by capacitance-voltage measurements. A statistical study carried out on single wires shows the consistency of the doping profile values measured for individual microwires compared to assemblies of hundreds of wires processed on the same sample. The robustness of this method is then demonstrated on four epitaxial structures with different growth and doping conditions. Finally, electron-beam-induced current and secondary electron profiles are used to validate the depletion region width and the position in the core-shell structure.

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.

Morphology Transition of ZnO from Thin Film to Nanowires on Silicon and its Correlated Enhanced Zinc Polarity Uniformity and Piezoelectric Responses.

ZnO thin films and nanostructures have received increasing interest in the field of piezoelectricity over the last decade, but their formation mechanisms on silicon when using pulsed-liquid injection metal-organic chemical vapor deposition (PLI-MOCVD) are still open to a large extent. Also, the effects of their morphology, dimensions, polarity, and electrical properties on their piezoelectric properties have not been completely decoupled yet. By only tuning the growth temperature from 400 to 750 °C while fixing the other growth conditions, the morphology transition of ZnO deposits on silicon from stacked thin films to nanowires through columnar thin films is shown. A detailed analysis of their formation mechanisms is further provided. The present transition is associated with strong enhancement of their crystallinity and growth texture along the c-axis together with a massive relaxation of the strain in nanowires. It is also related to a prevailed zinc polarity, for which its uniformity is strongly improved in nanowires. The nucleation of basal-plane stacking faults of I1-type in nanowires is also revealed and related to an emission line at about 3.326 eV in cathodoluminescence spectra, further exhibiting fairly low phonon coupling. Interestingly, the transition is additionally associated with a significant improvement of the piezoelectric amplitude, as determined by piezoresponse force microscopy measurements. The Zn-polar domains exhibit a larger piezoelectric amplitude than the O-polar domains, showing the importance of controlling the polarity in these deposits as a prerequisite to enhance the performances of piezoelectric devices. The present findings demonstrate the high potential in using the PLI-MOCVD system to form ZnO with different morphologies and polarity uniformity on silicon. They further reveal unambiguously the superiority of nanowires over thin films for piezoelectric devices.

Schottky Contacts on Polarity-Controlled Vertical ZnO Nanorods.

Polarity-controlled growth of ZnO by chemical bath deposition provides a method for controlling the crystal orientation of vertical nanorod arrays. The ability to define the morphology and structure of the nanorods is essential to maximizing the performance of optical and electrical devices such as piezoelectric nanogenerators; however, well-defined Schottky contacts to the polar facets of the structures have yet to be explored. In this work, we demonstrate a process to fabricate metal-semiconductor-metal device structures from vertical arrays with Au contacts on the uppermost polar facets of the nanorods and show that the O-polar nanorods (∼0.44 eV) have a greater effective barrier height than the Zn-polar nanorods (∼0.37 eV). Oxygen plasma treatment is shown by cathodoluminescence spectroscopy to affect midgap defects associated with radiative emissions, which improves the Schottky contacts from weakly rectifying to strongly rectifying. Interestingly, the plasma treatment is shown to have a much greater effect in reducing the number of carriers in O-polar nanorods through quenching of the donor-type substitutional hydrogen on oxygen sites (HO) when compared to the zinc-vacancy-related hydrogen defect complexes (VZn-nH) in Zn-polar nanorods that evolve to lower-coordinated complexes. The effect on HO in the O-polar nanorods coincides with a large reduction in the visible-range defects, producing a lower conductivity and creating the larger effective barrier heights. This combination can allow radiative losses and charge leakage to be controlled, enhancing devices such as dynamic photodetectors, strain sensors, and light-emitting diodes while showing that the O-polar nanorods can outperform Zn-polar nanorods in such applications.

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.

Exciton diffusion coefficient measurement in ZnO nanowires under electron beam irradiation.

In semiconductor nanowires (NWs) the exciton diffusion coefficient can be determined using a scanning electron microscope fitted with a cathodoluminescence system. High spatial and temporal resolution cathodoluminescence experiments are needed to measure independently the exciton diffusion length and lifetime in single NWs. However, both diffusion length and lifetime can be affected by the electron beam bombardment during observation and measurement. Thus, in this work the exciton lifetime in a ZnO NW is measured versus the electron beam dose (EBD) via a time-resolved cathodoluminescence experiment with a temporal resolution of 50 ps. The behavior of the measured exciton lifetime is consistent with our recent work on the EBD dependence of the exciton diffusion length in similar NWs investigated under comparable SEM conditions. Combining the two results, the exciton diffusion coefficient in ZnO is determined at room temperature and is found constant over the full span of EBD.

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.

In situ biasing and off-axis electron holography of a ZnO nanowire.

Quantitative characterization of electrically active dopants and surface charges in nano-objects is challenging, since most characterization techniques using electrons [1-3], ions [4] or field ionization effects [5-7] study the chemical presence of dopants, which are not necessarily electrically active. We perform cathodoluminescence and voltage contrast experiments on a contacted and biased ZnO nanowire with a Schottky contact and measure the depletion length as a function of reverse bias. We compare these results with state-of-the-art off-axis electron holography in combination with electrical in situ biasing on the same nanowire. The extension of the depletion length under bias observed in scanning electron microscopy based techniques is unusual as it follows a linear rather than square root dependence, and is therefore difficult to model by bulk equations or finite element simulations. In contrast, the analysis of the axial depletion length observed by holography may be compared with three-dimensional simulations, which allows estimating an n-doping level of 1 × 1018 cm-3 and negative sidewall surface charge of 2.5 × 1012 cm-2 of the nanowire, resulting in a radial surface depletion to a depth of 36 nm. We found excellent agreement between the simulated diameter of the undepleted core and the active thickness observed in the experimental data. By combining TEM holography experiments and finite element simulation of the NW electrostatics, the bulk-like character of the nanowire core is revealed.

Electron beam dose dependence of surface recombination velocity and surface space charge in semiconductor nanowires.

The characterization of nanowires (NWs) often requires the use of scanning electron beam techniques because of their high spatial resolution. However, the impact of the high energetic electron beam on the physical parameters under investigation is rarely taken into account. In this work, a combination of optical and electrical techniques is involved for the measurement of the electron beam dose (EBD) dependence of cathodoluminescence intensity, exciton diffusion length and electrical resistance in ZnO NWs. Large EBD dependences of these key parameters are observed and their reversibility is investigated. The results are discussed in terms of bulk and surface reversible modifications. In particular, the behaviors of surface recombination velocity and surface space charge under electron beam exposure are determined and simulated. This study points out that caution must be taken and experimental protocols must be well defined when measuring physical parameters of NWs using electron beam techniques.

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.

Spontaneous shape transition of thin films into ZnO nanowires with high structural and optical quality.

ZnO nanowires are usually formed by physical and chemical deposition techniques following the bottom-up approach consisting in supplying the reactants on a nucleation surface heated at a given temperature. We demonstrate an original alternative approach for the formation of ZnO nanowire arrays with high structural and optical quality, which is based on the spontaneous transformation of a ZnO thin film deposited by sol-gel process following a simple annealing. The development of these ZnO nanowires occurs through successive shape transitions, including the intermediate formation of pyramid-shaped islands. Their nucleation under near-equilibrium conditions is expected to be governed by thermodynamic considerations via the total free energy minimization related to the nanowire shape. It is further strongly assisted by the drastic reordering of the matter and by recrystallization phenomena through the massive transport of zinc and oxygen atoms towards the localized growth areas. The spontaneous shape transition process thus combines the easiness and low-cost of sol-gel process and simple annealing with the assets of the vapor phase deposition techniques. These findings cast a light on the fundamental mechanisms driving the spontaneous formation of ZnO nanowires and, importantly, reveal the great technological potential of the spontaneous shape transition process as a promising alternative approach to the more usual bottom-up approach.

Selective area growth of well-ordered ZnO nanowire arrays with controllable polarity.

Controlling the polarity of ZnO nanowires in addition to the uniformity of their structural morphology in terms of position, vertical alignment, length, diameter, and period is still a technological and fundamental challenge for real-world device integration. In order to tackle this issue, we specifically combine the selective area growth on prepatterned polar c-plane ZnO single crystals using electron-beam lithography, with the chemical bath deposition. The formation of ZnO nanowires with a highly controlled structural morphology and a high optical quality is demonstrated over large surface areas on both polar c-plane ZnO single crystals. Importantly, the polarity of ZnO nanowires can be switched from O- to Zn-polar, depending on the polarity of prepatterned ZnO single crystals. This indicates that no fundamental limitations prevent ZnO nanowires from being O- or Zn-polar. In contrast to their catalyst-free growth by vapor-phase deposition techniques, the possibility to control the polarity of ZnO nanowires grown in solution is remarkable, further showing the strong interest in the chemical bath deposition and hydrothermal techniques. The single O- and Zn-polar ZnO nanowires additionally exhibit distinctive cathodoluminescence spectra. To a broader extent, these findings open the way to the ultimate fabrication of well-organized heterostructures made from ZnO nanowires, which can act as building blocks in a large number of electronic, optoelectronic, and photovoltaic devices.

Carrier depletion and exciton diffusion in a single ZnO nanowire.

Carrier depletion and transport in a single ZnO nanowire Schottky device have been investigated at 5 K, using cathodoluminescence measurements. An exciton diffusion length of 200 nm has been determined along the nanowire axis. The depletion width is found to increase linearly with the reverse bias. The origin of this unusual dependence in semiconductor material is discussed in terms of charge location and dimensional effects on the screening of the junction electric field.

A single-step electron beam lithography of buried nanostructures using cathodoluminescence imaging and low temperature.

We report a new electron beam lithography process using the cathodoluminescence properties of semiconductors to visualize nanostructures buried underneath the resist and to subsequently write the pattern associated with these nanostructures. This single-step process could be used, for example, to make electrical contacts to nanowires (as illustrated in this work) or to design a photonic crystal resonator centered on a single quantum dot. Fabrication speed and positioning accuracy are significantly increased as compared to the standard process since no alignment marks and the mapping step of the nanostructures with respect to these marks are needed. We show also that low temperature (down to 5 K) could be used to improve the observation of the nanostructures through the resist while keeping very good spatial resolution.