Investigation of the Impact of Point Defects in InGaN/GaN Quantum Wells with High Dislocation Densities.

In this work, we report on the efficiency of single InGaN/GaN quantum wells (QWs) grown on thin (<1 µm) GaN buffer layers on silicon (111) substrates exhibiting very high threading dislocation (TD) densities. Despite this high defect density, we show that QW emission efficiency significantly increases upon the insertion of an In-containing underlayer, whose role is to prevent the introduction of point defects during the growth of InGaN QWs. Hence, we demonstrate that point defects play a key role in limiting InGaN QW efficiency, even in samples where their density (2-3 × 109 cm-2) is much lower than that of TD (2-3 × 1010 cm-2). Time-resolved photoluminescence and cathodoluminescence studies confirm the prevalence of point defects over TDs in QW efficiency. Interestingly, TD terminations lead to the formation of independent domains for carriers, thanks to V-pits and step bunching phenomena.

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.

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.

Molecular Origin of the Asymmetric Photoluminescence Spectra of CsPbBr3 at Low Temperature.

CsPbBr3 has received wide attention due to its superior emission yield and better thermal stability compared to other organic-inorganic lead halide perovskites. In this study, through an interplay of theory and experiments, we investigate the molecular origin of the asymmetric low-temperature photoluminescence spectra of CsPbBr3. We conclude that the origin of this phenomenon lies in a local dipole moment (and the induced Stark effect) due to the preferential localization of Cs+ in either of two off-center positions of the empty space between the surrounding PbBr6 octahedra. With increasing temperature, Cs+ ions are gradually occupying positions closer and closer to the center of the cavities. The gradual loss of ordering in the Cs+ position with increasing temperature is the driving force for the formation of tetragonal-like arrangements within the orthorhombic lattice.

UV Emission from GaN Wires with m-Plane Core-Shell GaN/AlGaN Multiple Quantum Wells.

The present work reports high-quality nonpolar GaN/Al0.6Ga0.4N multiple quantum wells (MQWs) grown in core-shell geometry by metal-organic vapor-phase epitaxy on the m-plane sidewalls of c̅-oriented hexagonal GaN wires. Optical and structural studies reveal ultraviolet (UV) emission originating from the core-shell GaN/AlGaN MQWs. Tuning the m-plane GaN QW thickness from 4.3 to 0.7 nm leads to a shift of the emission from 347 to 292 nm, consistent with Schrödinger-Poisson calculations. The evolution of the luminescence with temperature displays signs of strong localization, especially for samples with thinner GaN QWs and no evidence of quantum-confined Stark effect, as expected for nonpolar m-plane surfaces. The internal quantum efficiency derived from the photoluminescence (PL) intensity ratio at low and room temperatures is maximum (∼7.3% measured at low power excitation) for 2.6 nm thick quantum wells, emitting at 325 nm, and shows a large drop for thicker QWs. An extensive study of the PL quenching with temperature is presented. Two nonradiative recombination paths are activated at different temperatures. The low-temperature path is found to be intrinsic to the heterostructure, whereas the process that dominates at high temperature depends on the QW thickness and is strongly enhanced for QWs larger than 2.6 nm, causing a rapid decrease in the internal quantum efficiency.

Role of Underlayer for Efficient Core-Shell InGaN QWs Grown on m-plane GaN Wire Sidewalls.

Different types of buffer layers such as InGaN underlayer (UL) and InGaN/GaN superlattices are now well-known to significantly improve the efficiency of c-plane InGaN/GaN-based light-emitting diodes (LEDs). The present work investigates the role of two different kinds of pregrowth layers (low In-content InGaN UL and GaN UL namely "GaN spacer") on the emission of the core-shell m-plane InGaN/GaN single quantum well (QW) grown around Si-doped c̅-GaN microwires obtained by silane-assisted metal organic vapor phase epitaxy. According to photo- and cathodoluminescence measurements performed at room temperature, an improved efficiency of light emission at 435 nm with internal quantum efficiency >15% has been achieved by adding a GaN spacer prior to the growth of QW. As revealed by scanning transmission electron microscopy, an ultrathin residual layer containing Si located at the wire sidewall surfaces favors the formation of high density of extended defects nucleated at the first InGaN QW. This contaminated residual incorporation is buried by the growth of the GaN spacer and avoids the structural defect formation, therefore explaining the improved optical efficiency. No further improvement is observed by adding the InGaN UL to the structure, which is confirmed by comparable values of the effective carrier lifetime estimated from time-resolved experiments. Contrary to the case of planar c-plane QW where the improved efficiency is attributed to a strong decrease of point defects, the addition of an InGaN UL seems to have no influence in the case of radial m-plane QW.

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.

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.

Insights about the Absence of Rb Cation from the 3D Perovskite Lattice: Effect on the Structural, Morphological, and Photophysical Properties and Photovoltaic Performance.

Efficiencies >20% are obtained from the perovskite solar cells (PSCs) employing Cs+ and Rb+ based perovskite compositions; therefore, it is important to understand the effect of these inorganic cations specifically Rb+ on the properties of perovskite structures. Here the influence of Cs+ and Rb+ is elucidated on the structural, morphological, and photophysical properties of perovskite structures and the photovoltaic performances of resulting PSCs. Structural, photoluminescence (PL), and external quantum efficiency studies establish the incorporation of Cs+ (x < 10%) but amply rule out the possibility of Rb-incorporation into the MAPbI3 (MA = CH3 NH3+ ) lattice. Moreover, morphological studies and time-resolved PL show that both Cs+ and Rb+ detrimentally affect the surface coverage of MAPbI3 layers and charge-carrier dynamics, respectively, by influencing nucleation density and by inducing nonradiative recombination. In addition, differential scanning calorimetry shows that the transition from orthorhombic to tetragonal phase occurring around 160 K requires more thermal energy for the Cs-containing MAPbI3 systems compared to the pristine MAPbI3 . Investigation including mixed halide (I/Br) and mixed cation A-cation based compositions further confirms the absence of Rb+ from the 3D-perovskite lattice. The fundamental insights gained through this work will be of great significance to further understand highly promising perovskite compositions.

Intrinsic and Extrinsic Stability of Formamidinium Lead Bromide Perovskite Solar Cells Yielding High Photovoltage.

We report on both the intrinsic and the extrinsic stability of a formamidinium lead bromide [CH(NH2)2PbBr3 = FAPbBr3] perovskite solar cell that yields a high photovoltage. The fabrication of FAPbBr3 devices, displaying an outstanding photovoltage of 1.53 V and a power conversion efficiency of over 8%, was realized by modifying the mesoporous TiO2-FAPbBr3 interface using lithium treatment. Reasons for improved photovoltaic performance were revealed by a combination of techniques, including photothermal deflection absorption spectroscopy (PDS), transient-photovoltage and charge-extraction analysis, and time-integrated and time-resolved photoluminescence. With lithium-treated TiO2 films, PDS reveals that the TiO2-FAPbBr3 interface exhibits low energetic disorder, and the emission dynamics showed that electron injection from the conduction band of FAPbBr3 into that of mesoporous TiO2 is faster than for the untreated scaffold. Moreover, compared to the device with pristine TiO2, the charge carrier recombination rate within a device based on lithium-treated TiO2 film is 1 order of magnitude lower. Importantly, the operational stability of perovskites solar cells examined at a maximum power point revealed that the FAPbBr3 material is intrinsically (under nitrogen) as well as extrinsically (in ambient conditions) stable, as the unsealed devices retained over 95% of the initial efficiency under continuous full sun illumination for 150 h in nitrogen and dry air and 80% in 60% relative humidity (T = ∼60 °C). The demonstration of high photovoltage, a record for FAPbBr3, together with robust stability renders our work of practical significance.

Origin of unusual bandgap shift and dual emission in organic-inorganic lead halide perovskites.

Emission characteristics of metal halide perovskites play a key role in the current widespread investigations into their potential uses in optoelectronics and photonics. However, a fundamental understanding of the molecular origin of the unusual blueshift of the bandgap and dual emission in perovskites is still lacking. In this direction, we investigated the extraordinary photoluminescence behavior of three representatives of this important class of photonic materials, that is, CH3NH3PbI3, CH3NH3PbBr3, and CH(NH2)2PbBr3, which emerged from our thorough studies of the effects of temperature on their bandgap and emission decay dynamics using time-integrated and time-resolved photoluminescence spectroscopy. The low-temperature (<100 K) photoluminescence of CH3NH3PbI3 and CH3NH3PbBr3 reveals two distinct emission peaks, whereas that of CH(NH2)2PbBr3 shows a single emission peak. Furthermore, irrespective of perovskite composition, the bandgap exhibits an unusual blueshift by raising the temperature from 15 to 300 K. Density functional theory and classical molecular dynamics simulations allow for assigning the additional photoluminescence peak to the presence of molecularly disordered orthorhombic domains and also rationalize that the unusual blueshift of the bandgap with increasing temperature is due to the stabilization of the valence band maximum. Our findings provide new insights into the salient emission properties of perovskite materials, which define their performance in solar cells and light-emitting devices.

Triazatruxene-Based Hole Transporting Materials for Highly Efficient Perovskite Solar Cells.

Four center symmetrical star-shaped hole transporting materials (HTMs) comprising planar triazatruxene core and electron-rich methoxy-engineered side arms have been synthesized and successfully employed in (FAPbI3)0.85(MAPbBr3)0.15 perovskite solar cells. These HTMs are obtained from relatively cheap starting materials by adopting facile preparation procedure, without using expensive and complicated purification techniques. Developed compounds have suitable highest occupied molecular orbitals (HOMO) with respect to the valence band level of the perovskite, and time-resolved photoluminescence indicates that hole injection from the valence band of perovskite into the HOMO of triazatruxene-based HTMs is relatively more efficient as compared to that of well-studied spiro-OMeTAD. Remarkable power conversion efficiency over 18% was achieved using 5,10,15-trihexyl-3,8,13-tris(4-methoxyphenyl)-10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazole (KR131) with compositive perovskite absorber. This result demonstrates triazatruxene-based compounds as a new class of HTM for the fabrication of highly efficient perovskite solar cells.

Color control of nanowire InGaN/GaN light emitting diodes by post-growth treatment.

Core/shell InGaN/GaN nanowire light emitting diodes (LEDs) based on vertically standing single nanowires and nanowire arrays were fabricated and extensively characterized. The emission of single wire LEDs with the same conformal contact geometry as the array device exhibits the same broadening as the array LED electroluminescence, which proves an excellent wire-to-wire homogeneity. The electroluminescence spectra present two peaks corresponding to the m-plane InGaN quantum well (blue emission) and to an In-rich region at the m-plane-semipolar plane junction (green emission), in agreement with structural characterizations. Modification of the contact layout and a post-growth plasma treatment enable strongly suppressing the unwanted green electroluminescence while increasing the intensity in the blue spectral range for the same injected electrical power. Electron beam induced current mapping proves the inhibition of the electrical activity of the top part of the nanowire after plasma treatment. Inductively coupled plasma etching of the In-rich region permits one to completely remove the green emission for all injection currents, but loss of intensity in the blue spectral range is observed. Selectively contacting the m-plane and plasma treatment of the top part of the nanowire appear as a viable solution for controlling the color of core/shell nanowire LEDs with an inhomogeneous indium composition.

Biexcitonic molecules survive excitons at the Mott transition.

When the carrier density is increased in a semiconductor, according to the predictions of Sir Nevil Mott, a transition should occur from an insulating state consisting of a gas of excitons to a conductive electron-hole plasma. This crossover, usually referred to as the Mott transition, is driven by the mutual effects of phase-space filling and Coulomb screening because of the presence of other charges nearby. It drastically affects the optical and electrical characteristics of semiconductors and may, for example, drive the transition from a polariton laser to a vertical cavity surface-emitting laser. Usually, the possible existence of excitonic molecules (or biexcitons) is neglected in the understanding of the Mott transition because the biexciton is supposed to be less robust against screening effects. Here, against common beliefs, we observe that the biexciton in a GaN quantum well is more stable towards the Mott transition than the exciton.

Exciton drift in semiconductors under uniform strain gradients: application to bent ZnO microwires.

Optimizing the electronic structures and carrier dynamics in semiconductors at atomic scale is an essential issue for innovative device applications. Besides the traditional chemical doping and the use of homo/heterostructures, elastic strain has been proposed as a promising possibility. Here, we report on the direct observation of the dynamics of exciton transport in a ZnO microwire under pure elastic bending deformation, by using cathodoluminescence with high temporal, spatial, and energy resolutions. We demonstrate that excitons can be effectively drifted by the strain gradient in inhomogeneous strain fields. Our observations are well reproduced by a drift-diffusion model taking into account the strain gradient and allow us to deduce an exciton mobility of 1400 ± 100 cm(2)/(eV s) in the ZnO wire. These results propose a way to tune the exciton dynamics in semiconductors and imply the possible role of strain gradient in optoelectronic and sensing nano/microdevices.

Coupling atom probe tomography and photoluminescence spectroscopy: exploratory results and perspectives.

The development of laser-assisted atom probes makes it possible, in principle, to exploit the femtosecond laser pulse not only for triggering ion evaporation from a nanometric field emission tip, but also for generating photons via the radiative recombination of electron-hole pairs in tips made of dielectric materials. In this article we demonstrate a first step towards a correlation of micro-photoluminescence (µ-PL) and laser-assisted tomographic atom probe (LA-TAP) analysis applied separately on the same objects, namely on ZnO microwires. In particular, we assess that the use of the focused ion beam (FIB) tip preparation method significantly degrades the radiative recombination yield of the analyzed microwires. We discuss the strategies to avoid the FIB-induced damage on the optical properties of the sample and how to get beyond the correlated µ-PL and LA-TAP analysis with a coupled approach allowing to perform the two analyses within the same instrument.

Self-assembled GaN quantum wires on GaN/AlN nanowire templates.

We present a novel approach for self-assembled growth of GaN quantum wires (QWRs) exhibiting strong confinement in two spatial dimensions. The GaN QWRs are formed by selective nucleation on {112[combining macron]0} (a-plane) facets formed at the six intersections of {11[combining macron]00} (m-plane) sidewalls of AlN/GaN nanowires used as a template. Based on microscopy observations we have developed a 3D model explaining the growth mechanism of QWRs. We show that the QWR formation is governed by self-limited pseudomorphic growth on the side facets of the nanowires (NWs). Quantum confinement in the QWRs is confirmed by the observation of narrow photoluminescence lines originating from individual QWRs with emission energies up to 4.4 eV. Time-resolved photoluminescence studies reveal a short decay time (~120 ps) of the QWR emission. Capping of the QWRs with AlN allows enhancement of the photoluminescence, which is blue-shifted due to compressive strain. The emission energies from single QWRs are modelled assuming a triangular cross-section resulting from self-limited growth on a-plane facets. Comparison with the experimental results yields an average QWR diameter of about 2.7 nm in agreement with structural characterization. The presented results open a new route towards controlled realization of one-dimensional semiconductor quantum structures with a high potential both for fundamental studies and for applications in electronics and in UV light generation.

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.