Low-Cost, High-Yield ZnO Nanostars Synthesis for Pseudocapacitor Applications.

Energy storage devices based on earth-abundant materials are key steps towards portable and sustainable technologies used in daily life. Pseudocapacitive devices, combining high power and high energy density features, are widely required, and transition metal oxides represent promising building materials owing to their excellent stability, abundance, and ease of synthesis. Here, we report an original ZnO-based nanostructure, named nanostars (NSs), obtained at high yields by chemical bath deposition (CBD) and applied as pseudocapacitors. The ZnO NSs appeared as bundles of crystalline ZnO nanostrips (30 nm thin and up to 12 µm long) with a six-point star shape, self-assembled onto a plane. X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence spectroscopy (PL) were used to confirm the crystal structure, shape, and defect-mediated radiation. The ZnO NSs, dispersed onto graphene paper, were tested for energy storage by cyclic voltammetry (CV) and galvanostatic charge−discharge (GCD) analyses, showing a clear pseudocapacitor behavior. The energy storage mechanism was analyzed and related to oxygen vacancy defects at the surface. A proper evaluation of the charge stored on the ZnO NSs and the substrate allowed us to investigate the storage efficiency, measuring a maximum specific capacitance of 94 F g−1 due to ZnO nanostars alone, with a marked diffusion-limited behavior. The obtained results demonstrate the promising efficacy of ZnO-based NSs as sustainable materials for pseudocapacitors.

Morphological and Compositional Studies on Al/Ti/TiN/Si, Al/TiN/Si, Al/W/Si, Al/WN/Si Systems to Test the Diffusion Barrier Properties of Nanoscale-Thick Layers between Al and Si.

In this work, an investigation of the properties of nanoscale-thick Ti/TiN, TiN, W, WN layers as diffusion barriers between Si and Al is carried out in view of Si-based electronic applications. Heat treatments were performed on the samples to activate interdiffusion between Si and Al. Changing annealing time and temperature, each sample was morphologically characterized by scanning electron microscopy and atomic force microscopy and compositionally characterized by Rutherford backscattering analysis. The aim is to evaluate the efficiency of the layers as diffusion barriers between Si and Al and, at the same time, to evaluate the surface morphological changes upon annealing processes.

Stress evolution of Ge nanocrystals in dielectric matrices.

Germanium nanocrystals (Ge NCs) embedded in single and multilayer silicon oxide and silicon nitride matrices have been synthesized using plasma enhanced chemical vapor deposition followed by conventional furnace annealing or rapid thermal processing in N2 ambient. Compositions of the films were determined by Rutherford backscattering spectrometry and x-ray photoelectron spectroscopy. The formation of NCs under suitable process conditions was observed with high resolution transmission electron microscope micrographs and Raman spectroscopy. Stress measurements were done using Raman shifts of the Ge optical phonon line at 300.7 cm-1. The effect of the embedding matrix and annealing methods on Ge NC formation were investigated. In addition to Ge NCs in single layer samples, the stress on Ge NCs in multilayer samples was also analyzed. Multilayers of Ge NCs in a silicon nitride matrix separated by dielectric buffer layers to control the size and density of NCs were fabricated. Multilayers consisted of SiN y :Ge ultrathin films sandwiched between either SiO2 or Si3N4 by the proper choice of buffer material. We demonstrated that it is possible to tune the stress state of Ge NCs from compressive to tensile, a desirable property for optoelectronic applications. We also observed that there is a correlation between the stress and the crystallization threshold in which the compressive stress enhances the crystallization, while the tensile stress suppresses the process.

Broadband photocurrent enhancement in a-Si:H solar cells with plasmonic back reflectors.

Plasmonic light trapping in thin film silicon solar cells is a promising route to achieve high efficiency with reduced volumes of semiconductor material. In this paper, we study the enhancement in the opto-electronic performance of thin a-Si:H solar cells due to the light scattering effects of plasmonic back reflectors (PBRs), composed of self-assembled silver nanoparticles (NPs), incorporated on the cells' rear contact. The optical properties of the PBRs are investigated according to the morphology of the NPs, which can be tuned by the fabrication parameters. By analyzing sets of solar cells built on distinct PBRs we show that the photocurrent enhancement achieved in the a-Si:H light trapping window (600 - 800 nm) stays in linear relation with the PBRs diffuse reflection. The best-performing PBRs allow a pronounced broadband photocurrent enhancement in the cells which is attributed not only to the plasmon-assisted light scattering from the NPs but also to the front surface texture originated from the conformal growth of the cell material over the particles. As a result, remarkably high values of J(sc) and V(oc) are achieved in comparison to those previously reported in the literature for the same type of devices.

Laser irradiation of ZnO:Al/Ag/ZnO:Al multilayers for electrical isolation in thin film photovoltaics.

Laser irradiation of ZnO:Al/Ag/ZnO:Al transparent contacts is investigated for segmentation purposes. The quality of the irradiated areas has been experimentally evaluated by separation resistance measurements, and the results are complemented with a thermal model used for numerical simulations of the laser process. The presence of the Ag interlayer plays two key effects on the laser scribing process by increasing the maximum temperature reached in the structure and accelerating the cool down process. These evidences can promote the use of ultra-thin ZnO:Al/Ag/ZnO:Al electrode in large-area products, such as for solar modules.

Self-assembled silver nanoparticles for plasmon-enhanced solar cell back reflectors: correlation between structural and optical properties.

The spectra of localized surface plasmon resonances (LSPRs) in self-assembled silver nanoparticles (NPs), prepared by solid-state dewetting of thin films, are discussed in terms of their structural properties. We summarize the dependences of size and shape of NPs on the fabrication conditions with a proposed structural-phase diagram. It was found that the surface coverage distribution and the mean surface coverage (SC) size were the most appropriate statistical parameters to describe the correlation between the morphology and the optical properties of the nanostructures. The results are interpreted with theoretical predictions based on Mie theory. The broadband scattering efficiency of LSPRs in the nanostructures is discussed towards application as plasmon-enhanced back reflectors in thin-film solar cells.

Room-temperature efficient light detection by amorphous Ge quantum wells.

In this work, ultrathin amorphous Ge films (2 to 30 nm in thickness) embedded in SiO2 layers were grown by magnetron sputtering and employed as proficient light sensitizer in photodetector devices. A noteworthy modification of the visible photon absorption is evidenced due to quantum confinement effects which cause both a blueshift (from 0.8 to 1.8 eV) in the bandgap and an enhancement (up to three times) in the optical oscillator strength of confined carriers. The reported quantum confinement effects have been exploited to enhance light detection by Ge quantum wells, as demonstrated by photodetectors with an internal quantum efficiency of 70%.

The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica.

The usage of semiconductor nanostructures is highly promising for boosting the energy conversion efficiency in photovoltaics technology, but still some of the underlying mechanisms are not well understood at the nanoscale length. Ge quantum dots (QDs) should have a larger absorption and a more efficient quantum confinement effect than Si ones, thus they are good candidate for third-generation solar cells. In this work, Ge QDs embedded in silica matrix have been synthesized through magnetron sputtering deposition and annealing up to 800°C. The thermal evolution of the QD size (2 to 10 nm) has been followed by transmission electron microscopy and X-ray diffraction techniques, evidencing an Ostwald ripening mechanism with a concomitant amorphous-crystalline transition. The optical absorption of Ge nanoclusters has been measured by spectrophotometry analyses, evidencing an optical bandgap of 1.6 eV, unexpectedly independent of the QDs size or of the solid phase (amorphous or crystalline). A simple modeling, based on the Tauc law, shows that the photon absorption has a much larger extent in smaller Ge QDs, being related to the surface extent rather than to the volume. These data are presented and discussed also considering the outcomes for application of Ge nanostructures in photovoltaics.PACS: 81.07.Ta; 78.67.Hc; 68.65.-k.

Mechanism of boron diffusion in amorphous silicon.

We have elucidated the mechanism for B migration in the amorphous (a-) Si network. B diffusivity in a-Si is much higher than in crystalline Si; it is transient and increases with B concentration up to 2 x 10(20) B/cm(3). At higher density, B atoms in a-Si quickly precipitate. B diffusion is indirect, mediated by dangling bonds (DB) present in a-Si. The density of DB is enhanced by B accommodation in the a-Si network and decreases because of a-Si relaxation. Accurate data simulations allow one to extract the DB diffusivity, whose activation energy is 2.6 eV. Implications of these results are discussed.

Atomistic mechanism of boron diffusion in silicon.

B diffuses in crystalline Si by reacting with a Si self-interstitial (I) with a frequency g and so forming a fast migrating BI complex that can migrate for an average length lambda. We experimentally demonstrate that both g and lambda strongly depend on the free hole concentration p. At low p, g has a constant trend and lambda increases with p, while at high p, g has a superlinear trend and lambda decreases with p. This demonstrates that BI forms in the two regimes by interaction with neutral and double positive I, respectively, and its charge state has to change by interaction with free holes before diffusing.