Direct Band Gap AlGaAs Wurtzite Nanowires.

Wurtzite AlGaAs is a technologically promising yet unexplored material. Here we study it both experimentally and numerically. We develop a complete numerical model based on an 8-band k→·p→ method, including electromechanical fields, and calculate the optoelectronic properties of wurtzite AlGaAs nanowires with different Al content. We then compare them with our experimental data. Our results strongly suggest that wurtzite AlGaAs is a direct band gap material. Moreover, we have also numerically obtained the band gap of wurtzite AlAs and the valence band offset between AlAs and GaAs in the wurtzite symmetry.

Carrier transport and emission efficiency in InGaN quantum-dot based light-emitting diodes.

We present a study of blue III-nitride light-emitting diodes (LEDs) with multiple quantum well (MQW) and quantum dot (QD) active regions (ARs), comparing experimental and theoretical results. The LED samples were grown by metalorganic vapor phase epitaxy, utilizing growth interruption in the hydrogen/nitrogen atmosphere and variable reactor pressure to control the AR microstructure. Realistic configuration of the QD AR implied in simulations was directly extracted from HRTEM characterization of the grown QD-based structures. Multi-scale 2D simulations of the carrier transport inside the multiple QD AR have revealed a non-trivial pathway for carrier injection into the dots. Electrons and holes are found to penetrate deep into the multi-layer AR through the gaps between individual QDs and get into the dots via their side edges rather than via top and bottom interfaces. This enables a more homogeneous carrier distribution among the dots situated in different layers than among the laterally uniform quantum well (QWs) in the MQW AR. As a result, a lower turn-on voltage is predicted for QD-based LEDs, as compared to MQW ones. Simulations did not show any remarkable difference in the efficiencies of the MQW and QD-based LEDs, if the same recombination coefficients are utilized, i.e. a similar crystal quality of both types of LED structures is assumed. Measurements of the current-voltage characteristics of LEDs with both kinds of the AR have shown their close similarity, in contrast to theoretical predictions. This implies the conventional assumption of laterally uniform QWs not to be likely an adequate approximation for the carrier transport in MQW LED structures. Optical characterization of MQW and QD-based LEDs has demonstrated that the later ones exhibit a higher efficiency, which could be attributed to better crystal quality of the grown QD-based structures. The difference in the crystal quality explains the recently observed correlation between the growth pressure of LED structures and their efficiency and should be taken into account while further comparing performances of MQW and QD-based LEDs. In contrast to experimental results, our simulations did not reveal any advantages of using QD-based ARs over the MQW ones, if the same recombination constants are assumed for both cases. This fact demonstrates importance of accounting for growth-dependent factors, like crystal quality, which may limit the device performance. Nevertheless, a more uniform carrier injection into multi-layer QD ARs predicted by modeling may serve as the basis for further improvement of LED efficiency by lowering carrier density in individual QDs and, hence, suppressing the Auger recombination losses.

Influence of electromechanical coupling on optical properties of InGaN quantum-dot based light-emitting diodes.

The impact of electromechanical coupling on optical properties of light-emitting diodes (LEDs) with InGaN/GaN quantum-dot (QD) active regions is studied by numerical simulations. The structure, i.e. the shape and the average In content of the QDs, has been directly derived from experimental data on out-of-plane strain distribution obtained from the geometric-phase analysis of a high-resolution transmission electron microscopy image of an LED structure grown by metalorganic vapor-phase epitaxy. Using continuum [Formula: see text] calculations, we have studied first the lateral and full electromechanical coupling between the QDs in the active region and its impact on the emission spectrum of a single QD located in the center of the region. Our simulations demonstrate the spectrum to be weakly affected by the coupling despite the strong common strain field induced in the QD active region. Then we analyzed the effect of vertical coupling between vertically stacked QDs as a function of the interdot distance. We have found that QCSE gives rise to a blue-shift of the overall emission spectrum when the interdot distance becomes small enough. Finally, we compared the theoretical spectrum obtained from simulation of the entire active region with an experimental electroluminescence (EL) spectrum. While the theoretical peak emission wavelength of the selected central QD corresponded well to that of the EL spectrum, the width of the latter one was determined by the scatter in the structures of various QDs located in the active region. Good agreement between the simulations and experiment achieved as a whole validates our model based on realistic structure of the QD active region and demonstrates advantages of the applied approach.

Model of a realistic InP surface quantum dot extrapolated from atomic force microscopy results.

We report on numerical simulations of a zincblende InP surface quantum dot (QD) on In0.48Ga0.52 buffer. Our model is strictly based on experimental structures, since we extrapolated a three-dimensional dot directly by atomic force microscopy results. Continuum electromechanical, [Formula: see text] bandstructure and optical calculations are presented for this realistic structure, together with benchmark calculations for a lens-shape QD with the same radius and height of the extrapolated dot. Interesting similarities and differences are shown by comparing the results obtained with the two different structures, leading to the conclusion that the use of a more realistic structure can provide significant improvements in the modeling of QDs fact, the remarkable splitting for the electron p-like levels of the extrapolated dot seems to prove that a realistic experimental structure can reproduce the right symmetry and a correct splitting usually given by atomistic calculations even within the multiband [Formula: see text] approach. Moreover, the energy levels and the symmetry of the holes are strongly dependent on the shape of the dot. In particular, as far as we know, their wave function symmetries do not seem to resemble to any results previously obtained with simulations of zincblende ideal structures, such as lenses or truncated pyramids. The magnitude of the oscillator strengths is also strongly dependent on the shape of the dot, showing a lower intensity for the extrapolated dot, especially for the transition between the electrons and holes ground state, as a result of a relevant reduction of the wave functions overlap. We also compare an experimental photoluminescence spectrum measured on an homogeneous sample containing about 60 dots with a numerical ensemble average derived from single dot calculations. The broader energy range of the numerical spectrum motivated us to perform further verifications, which have clarified some aspects of the experimental results and helped us to develop a suitable model for the spectrum, by assuming a not equiprobable weight from each dot, a model which is extremely consistent with the experimental data.

State of the Art of Continuous and Atomistic Modeling of Electromechanical Properties of Semiconductor Quantum Dots.

The main intent of this paper is to present an exhaustive description of the most relevant mathematical models for the electromechanical properties of heterostructure quantum dots. Models are applied both to wurtzite and zincblende quantum dot due to the relevance they have shown for optoelectronic applications. In addition to a complete overview of the continuous and atomistic models for the electromechanical fields, analytical results will be presented for some relevant approximations, some of which are unpublished, such as models in cylindrical approximation or a cubic approximation for the transformation of a zincblende parametrization to a wurtzite one and vice versa. All analytical models will be supported by a wide range of numerical results, most of which are also compared with experimental measurements.

Model of a GaAs Quantum Dot in a Direct Band Gap AlGaAs Wurtzite Nanowire.

We present a study with a numerical model based on k→·p→, including electromechanical fields, to evaluate the electromechanical and optoelectronic properties of single GaAs quantum dots embedded in direct band gap AlGaAs nanowires. The geometry and the dimensions of the quantum dots, in particular the thickness, are obtained from experimental data measured by our group. We also present a comparison between the experimental and numerically calculated spectra to support the validity of our model.

Electromechanically Coupled III-N Quantum Dots.

We exploit the three-dimensional (3D) character of the strain field created around InGaN islands formed within the multilayer structures spaced by a less than 1-nm-thick GaN layer for the creation of spatially correlated electronically coupled quantum dots (QDs). The laterally inhomogeneous vertical out-diffusion of In atoms during growth interruption is the basic mechanism for the formation of InGaN islands within as-deposited 2D layers. An anisotropic 3D strain field created in the first layer is sufficient to justify the vertical correlation of the islands formed in the upper layers spaced by a sufficiently thin GaN layer. When the thickness of a GaN spacer exceeds 1 nm, QDs from different layers under the same growth conditions emit independently and in the same wavelength range. When extremely thin (less than 1 nm), a GaN spacer is formed solely by applying short GI, and a double wavelength emission in the blue and green spectral ranges evidences the electromechanical coupling. With k→·p→ calculations including electromechanical fields, we model the optoelectronic properties of a structure with three InGaN lens-shaped QDs embedded in a GaN matrix, with three different configurations of In content. The profiles of the band structures are strongly dependent on the In content arrangement, and the quantum-confined Stark effect is significantly reduced in a structure with an increasing gradient of In content from the top to the bottom QD. This configuration exhibits carrier tunneling through the QDs, an increase of wave functions overlap, and evidence emerges of three distinct peaks in the spectral range.

Vertically Aligned Nanowires and Quantum Dots: Promises and Results in Light Energy Harvesting.

The synthesis of crystals with a high surface-to-volume ratio is essential for innovative, high-performance electronic devices and sensors. The easiest way to achieve this in integrated devices with electronic circuits is through the synthesis of high-aspect-ratio nanowires aligned vertically to the substrate surface. Such surface structuring is widely employed for the fabrication of photoanodes for solar cells, either combined with semiconducting quantum dots or metal halide perovskites. In this review, we focus on wet chemistry recipes for the growth of vertically aligned nanowires and technologies for their surface functionalization with quantum dots, highlighting the procedures that yield the best results in photoconversion efficiencies on rigid and flexible substrates. We also discuss the effectiveness of their implementation. Among the three main materials used for the fabrication of nanowire-quantum dot solar cells, ZnO is the most promising, particularly due to its piezo-phototronic effects. Techniques for functionalizing the surfaces of nanowires with quantum dots still need to be refined to be effective in covering the surface and practical to implement. The best results have been obtained from slow multi-step local drop casting. It is promising that good efficiencies have been achieved with both environmentally toxic lead-containing quantum dots and environmentally friendly zinc selenide.

Impact of Local Composition on the Emission Spectra of InGaN Quantum-Dot LEDs.

A possible solution for the realization of high-efficiency visible light-emitting diodes (LEDs) exploits InGaN-quantum-dot-based active regions. However, the role of local composition fluctuations inside the quantum dots and their effect of the device characteristics have not yet been examined in sufficient detail. Here, we present numerical simulations of a quantum-dot structure restored from an experimental high-resolution transmission electron microscopy image. A single InGaN island with the size of ten nanometers and nonuniform indium content distribution is analyzed. A number of two- and three-dimensional models of the quantum dot are derived from the experimental image by a special numerical algorithm, which enables electromechanical, continuum k→·p→, and empirical tight-binding calculations, including emission spectra prediction. Effectiveness of continuous and atomistic approaches are compared, and the impact of InGaN composition fluctuations on the ground-state electron and hole wave functions and quantum dot emission spectrum is analyzed in detail. Finally, comparison of the predicted spectrum with the experimental one is performed to assess the applicability of various simulation approaches.

Frenkel-Poole Mechanism Unveils Black Diamond as Quasi-Epsilon-Near-Zero Surface.

A recent innovation in diamond technology has been the development of the "black diamond" (BD), a material with very high optical absorption generated by processing the diamond surface with a femtosecond laser. In this work, we investigate the optical behavior of the BD samples to prove a near to zero dielectric permittivity in the high electric field condition, where the Frenkel-Poole (FP) effect takes place. Zero-epsilon materials (ENZ), which represent a singularity in optical materials, are expected to lead to remarkable developments in the fields of integrated photonic devices and optical interconnections. Such a result opens the route to the development of BD-based, novel, functional photonic devices.

Effect of dielectric Bragg grating nanostructuring on dye sensitized solar cells.

We report on a theoretical investigation on the influence of different wavelength scale periodic grating architectures on dye sensitized solar cell (DSC). A broadband absorption enhancement is expected in such solar cells thanks to diffraction effects produced by these structures. Their optimal size has been analyzed in terms of pitch grating, height and position along the solar cell layers. Numerical simulations indicate that nanostructuring the interface between the active and the electrolyte layer by integrating a dielectric grating produces an absorption enhancement of 23.4%. The presented results have been also evaluated in view of feasible realistic structures compatible with low cost soft lithographic techniques.

Effect of dielectric Bragg grating nanostructuring on dye sensitized solar cells.

We report on a theoretical investigation on the influence of different wavelength scale periodic grating architectures on dye sensitized solar cell (DSC). A broadband absorption enhancement is expected in such solar cells thanks to diffraction effects produced by these structures. Their optimal size has been analyzed in terms of pitch grating, height and position along the solar cell layers. Numerical simulations indicate that nanostructuring the interface between the active and the electrolyte layer by integrating a dielectric grating produces an absorption enhancement of 23.4%. The presented results have been also evaluated in view of feasible realistic structures compatible with low cost soft lithographic techniques.

Light-Trapping Electrode for the Efficiency Enhancement of Bifacial Perovskite Solar Cells.

Antireflection and light-trapping coatings are important parts of photovoltaic architectures, which enable the reduction of parasitic optical losses, and therefore increase the power conversion efficiency (PCE). Here, we propose a novel approach to enhance the efficiency of perovskite solar cells using a light-trapping electrode (LTE) with non-reciprocal optical transmission, consisting of a perforated metal film covered with a densely packed array of nanospheres. Our LTE combines charge collection and light trapping, and it can replace classical transparent conducting oxides (TCOs) such as ITO or FTO, providing better optical transmission and conductivity. One of the most promising applications of our original LTE is the optimization of efficient bifacial perovskite solar cells. We demonstrate that with our LTE, the short-circuit current density and fill factor are improved for both front and back illumination of the solar cells. Thus, we observe an 11% improvement in the light absorption for the monofacial PSCs, and a 15% for the bifacial PSCs. The best theoretical results of efficiency for our PSCs are 27.9% (monofacial) and 33.4% (bifacial). Our study opens new prospects for the further efficiency enhancement for perovskite solar cells.

Charge Transport Mechanisms of Black Diamond at Cryogenic Temperatures.

Black diamond is an emerging material for solar applications. The femtosecond laser surface treatment of pristine transparent diamond allows the solar absorptance to be increased to values greater than 90% from semi-transparency conditions. In addition, the defects introduced by fs-laser treatment strongly increase the diamond surface electrical conductivity and a very-low activation energy is observed at room temperature. In this work, the investigation of electronic transport mechanisms of a fs-laser nanotextured diamond surface is reported. The charge transport was studied down to cryogenic temperatures, in the 30−300 K range. The samples show an activation energy of a few tens of meV in the highest temperature interval and for T < 50 K, the activation energy diminishes to a few meV. Moreover, thanks to fast cycles of measurement, we noticed that the black-diamond samples also seem to show a behavior close to ferromagnetic materials, suggesting electron spin influence over the transport properties. The mentioned properties open a new perspective in designing novel diamond-based biosensors and a deep knowledge of the charge-carrier transport in black diamond becomes fundamental.

Fabry-Perot Pressure Sensors Based on Polycrystalline Diamond Membranes.

Pressure sensors based on diamond membranes were designed and tested for gas pressure measurement up to 6.8 MPa. The diamond film (2" diameter, 6 µm thickness)-grown by microwave plasma chemical vapor deposition on a silicon substrate-was a starting material to produce an array of membranes with different diameters in the 130-400 µm range, in order to optimize the sensor performance. Each 5 mm × 5 mm sensing element was obtained by subsequent silicon slicing. The fixed film thickness, full-scale pressure range, and sensor sensitivity were established by a proper design of the diameter of diamond membrane which represents the sensing element for differential pressure measurement. The pressure-induced deflection of the membrane was optically measured using a Fabry-Pérot interferometer formed by a single mode optical fiber front surface and the deflecting diamond film surface. The optical response of the system was numerically simulated using geometry and the elastic properties of the diamond diaphragm, and was compared with the experiments. Depending on the diamond membrane's diameter, the fabricated sensors displayed a good modulation depth of response over different full-scale ranges, from 3 to 300 bar. In view of the excellent mechanical, thermal, and chemical properties of diamond, such pressure sensors could be useful for performance in a harsh environment.

Giant Enhancement of Radiative Recombination in Perovskite Light-Emitting Diodes with Plasmonic Core-Shell Nanoparticles.

The integration of nanoparticles (NPs) into functional materials is a powerful tool for the smart engineering of their physical properties. If properly designed and optimized, NPs possess unique optical, electrical, quantum, and other effects that will improve the efficiency of optoelectronic devices. Here, we propose a novel approach for the enhancement of perovskite light-emitting diodes (PeLEDs) based on electronic band structure deformation by core-shell NPs forming a metal-oxide-semiconductor (MOS) structure with an Au core and SiO2 shell located in the perovskite layer. The presence of the MOS interface enables favorable charge distribution in the active layer through the formation of hole transporting channels. For the PeLED design, we consider integration of the core-shell NPs in the realistic numerical model. Using our verified model, we show that, compared with the bare structure, the incorporation of NPs increases the radiative recombination rate of PeLED by several orders of magnitude. It is intended that this study will open new perspectives for further efficiency enhancement of perovskite-based optoelectronic devices with NPs.

Entropic algorithms and the lid method as exploration tools for complex landscapes.

Monte Carlo algorithms such as the Wang-Landau algorithm and similar "entropic" methods are able to accurately sample the density of states of model systems and thereby give access to thermal equilibrium properties at any temperature. Thermal equilibrium is, however, unachievable at low temperatures in glassy systems. Such systems are characterized by a multitude of metastable configurations pictorially referred to as "valleys" of an energy landscape. Geometrical properties of the landscape, e.g., the local density of states describing the distribution in energy of the states belonging to a single valley, are key to understanding the dynamical properties of such systems. In this paper we combine the lid algorithm, a tool for landscape exploration previously applied to a range of models, with the Wang-Swendsen algorithm. To test this improved exploration tool, we consider a paradigmatic complex system, the Edwards-Anderson model in two and three spatial dimensions. We find a striking difference between the energy dependence of the local density of states in two dimensions and three dimensions--nearly linear in the first case, and nearly exponential in the second. The dynamical consequences of these findings are discussed.