Real-time approach to the optical properties of solids and nanostructures: Time-dependent Bethe-Salpeter equation

Many-body effects are known to play a crucial role in the electronic and optical properties of solids and nanostructures. Nevertheless, the majority of theoretical and numerical approaches able to capture the influence of Coulomb correlations are restricted to the linear response regime. In this work, we introduce an approach based on a real-time solution of the electronic dynamics. The proposed approach reduces to the well-known Bethe-Salpeter equation in the linear limit regime and it makes it possible, at the same time, to investigate correlation effects in nonlinear phenomena. We show the flexibility and numerical stability of the proposed approach by calculating the dielectric constants and the effect of a strong pulse excitation in bulk h-BN.

Surface-Enhanced Raman Scattering from Metallic Nanostructures: Bridging the Gap between the Near-Field and Far-Field Responses

We present here a detailed study of the complex relationship between the electromagnetic near-field and far-field responses of "real" nanostructured metallic surfaces. The near-field and far-field responses are specified in terms of (spectra of) the surface-enhanced Raman-scattering enhancement factor (SERS EF) and optical extinction, respectively. First, it is shown that gold nanorod- and nanotube-array substrates exhibit three distinct localized surface plasmon resonances (LSPRs): a longitudinal, a transverse, and a cavity mode. The cavity mode simultaneously has the largest impact on the near-field behavior (as observed through the SERS EF) and the weakest optical interaction: It has a "near-field-type" character. The transverse and longitudinal modes have a significant impact on the far-field behavior but very little impact on SERS: They have a "far-field-type" character. We confirm the presence of the cavity mode using a combination of SERS EF spectra, electron microscopy, and electromagnetic modeling and thus clearly illustrate and explain the (lack of) correlation between the SERS EF spectra and the optical response in terms of the contrasting character of the three LSPRs. In doing so, we experimentally demonstrate that, for a surface that supports multiple LSPRs, the near-field and far-field properties can in fact be tuned almost independently. It is further demonstrated that small changes in geometrical parameters that tune the spectral location of the LPSRs can also drastically influence the character of these modes, resulting in certain unusual behavior, such as the far-field resonance redshift as the near-field resonance blueshifts. DOI: 10.1103/PhysRevX.3.011001

One-step synthesis of ZnO nanosheets: a blue-white fluorophore

Zinc oxide is synthesised at low temperature (80A degrees C) in nanosheet geometry using a substrate-free, single-step, wet-chemical method and is found to act as a blue-white fluorophore. Investigation by atomic force microscopy, electron microscopy, and X-ray diffraction confirms zinc oxide material of nanosheet morphology where the individual nanosheets are polycrystalline in nature with the crystalline structure being of wurtzite character. Raman spectroscopy indicates the presence of various defects, while photoluminescence measurements show intense green (centre wavelength approximately 515 nm) blue (approximately 450 nm), and less dominant red (approximately 640 nm) emissions due to a variety of vacancy and interstitial defects, mostly associated with surfaces or grain boundaries. The resulting colour coordinate on the CIE-1931 standard is (0.23, 0.33), demonstrating potential for use as a blue-white fluorescent coating in conjunction with ultraviolet emitting LEDs. Although the defects are often treated as draw-backs of ZnO, here we demonstrate useful broadband visible fluorescence properties in as-prepared ZnO. 

Unusual photoresponse of indium doped ZnO/organic thin film heterojunction

Photoresponse of n-type indium-doped ZnO and a p-type polymer (PEDOT:PSS) heterojunction devices are studied, juxtaposed with the photoluminescence of the In-ZnO samples. In addition to the expected photoresponse in the ultraviolet, the heterojunctions exhibit significant photoresponse to the visible (532 nm). However, neither the doped ZnO nor PEDOT: PSS individually show any photoresponse to visible light. The sub-bandgap photoresponse of the heterojunction originates from visible photon mediated e-h generation between the In-ZnO valence band and localized states lying within the band gap. Though increased doping of In-ZnO has limited effect on the photoluminescence, it significantly diminishes the photoresponse. The study indicates that optimally doped devices are promising for the detection of wavelengths in selected windows in the visible. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4704655]

Cobalt-doped ZnO nanowires on quartz: Synthesis by simple chemical method and characterization

The synthesis of cobalt-doped ZnO nanowires is achieved using a simple, metal salt decomposition growth technique. A sequence of drop casting on a quartz substrate held at 100 degrees C and annealing results in the growth of nanowires of average (modal) length similar to 200 nm and diameter of 15 +/- 4 nm and consequently an aspect ratio of similar to 13. A variation in the synthesis process, where the solution of mixed salts is deposited on the substrate at 25 degrees C, yields a grainy film structure which constitutes a useful comparator case. X-ray diffraction shows a preferred [0001] growth direction for the nanowires while a small unit cell volume contraction for Co-doped samples and data from Raman spectroscopy indicate incorporation of the Co dopant into the lattice; neither technique shows explicit evidence of cobalt oxides. Also the nanowire samples display excellent optical transmission across the entire visible range, as well as strong photoluminescence (exciton emission) in the near UV, centered at 3.25 eV. (C) 2012 Elsevier B.V. All rights reserved.

Performance of Nonlocal Optics When Applied to Plasmonic Nanostructures

Semiclassical nonlocal optics based on the hydrodynamic description of conduction electrons might be an adequate tool to study complex phenomena in the emerging field of nanoplasmonics. With the aim of confirming this idea, we obtain the local and nonlocal optical absorption spectra in a model nanoplasmonic device in which there are spatial gaps between the components at nanometric and subnanometric scales. After a comparison against time-dependent density functional calculations, we conclude that hydrodynamic nonlocal optics provides absorption spectra exhibiting qualitative agreement but not quantitative accuracy. This lack of accuracy, which is manifest even in the limit where induced electric currents are not established between the constituents of the device, is mainly due to the poor description of induced electron densities.

Manipulating Ferroelectric Domains in Nanostructures Under Electron Beams

Freestanding BaTiO3 nanodots exhibit domain structures characterized by distinct quadrants of ferroelastic 90 domains in transmission electron microscopy (TEM) observations. These differ significantly from flux-closure domain patterns in the same systems imaged by piezoresponse force microscopy. Based upon a series of phase field simulations of BaTiO3 nanodots, we suggest that the TEM patterns result from a radial electric field arising from electron beam charging of the nanodot. For sufficiently large charging, this converts flux-closure domain patterns to quadrant patterns with radial net polarizations. Not only does this explain the puzzling patterns that have been observed in TEM studies of ferroelectric nanodots, but also suggests how to manipulate ferroelectric domain patterns via electron beams.

Epitaxial BiFeO3 nanostructures fabricated by differential etching of BiFeO3 films

We report on differential etching behavior of the different orientations of the polarization in BiFeO3 (BFO), similar to other ferroelectrics, such as LiNbO3. We show how this effect can be used to fabricate epitaxial BiFeO3 nanostructures. By means of piezoresponse force microscopy (PFM) domains of arbitrary shape and size can be poled in an epitaxial BiFeO3 film, which are then reproduced in the film morphology by differential etching. Structures with a lateral size smaller than 200 nm were fabricated and very good retention properties as well as a highly increased piezoelectric response were detected by PFM. (C) 2011 American Institute of Physics. [doi:10.1063/1.3630027]

Ferroelectric nanostructures fabricated by focused-ion-beam milling in epitaxial BiFeO3 thin films

We studied a suitable route to fabricate ferroelectric islands by focused-ion-beam milling in bismuth ferrite epitaxial thin films. Piezoresponse force microscopy shows that the damage induced by the milling process is extended to 1 mu m away from the edge of the focused-ion-beam patterned islands. After a combined vacuum and oxygen atmosphere annealing procedure, ferroelectricity is fully recovered in structures with sizes down to 500 nm, while for 250 nm islands the defects at the interfaces induce polarization direction pinning.

Weathering tests of photocatalytic facade paints containing ZnO and TiO2.

The photocatalytic properties of self-cleaning acrylic paint containing TiO2 and ZnO were studied using Acid Orange 7 as a model compound. Paints were exposed to simulated weathering tests in a QUV panel. The initial photoactivity of the unweathered paints with ZnO was significantly higher. In the case of paints containing P25 the photocatalytic activity increases with weathering time, due to increasing destruction of the polymer resin and consequent exposure of the photocatalyst pigment to the Acid Orange 7 test solution. In contrast, in the case of paints containing ZnO, a decrease in photocatalytic activity is observed after weathering, due to the loss and/or photocorrosion of ZnO particles during the weathering process.

An in situ ionic-liquid-assisted synthetic approach to iron fluoride/graphene hybrid nanostructures as superior cathode materials for lithium ion batteries

A tactful ionic-liquid (IL)-assisted approach to in situ synthesis of iron fluoride/graphene nanosheet (GNS) hybrid nanostructures is developed. To ensure uniform dispersion and tight anchoring of the iron fluoride on graphene, we employ an IL which serves not only as a green fluoride source for the crystallization of iron fluoride nanoparticles but also as a dispersant of GNSs. Owing to the electron transfer highways created between the nanoparticles and the GNSs, the iron fluoride/GNS hybrid cathodes exhibit a remarkable improvement in both capacity and rate performance (230 mAh g^-1 at 0.1 C and 74 mAh g^-1 at 40 C). The stable adhesion of iron fluoride nanoparticles on GNSs also introduces a significant improvement in long-term cyclic performance (115 mAh g^-1 after 250 cycles even at 10 C). The superior electrochemical performance of these iron fluoride/GNS hybrids as lithium ion battery cathodes is ascribed to the robust structure of the hybrid and the synergies between iron fluoride nanoparticles and graphene. © 2013 American Chemical Society.

Dual interfacial modifications of hierarchically structured iodine-doped ZnO photoanodes for high-efficiency dye-sensitized solar cells

A nanocomposite porous electrode structure consisting of hierarchical iodine-doped zinc oxide (I-ZnO) aggregates combined with the two simple solution-processed interfacial modifications i.e. a ZnO compact layer (CL) and a TiO2 protective layer (PL) has been developed in order to understand electron transport and recombination in the photoanode matrix, together with boosting the conversion efficiency of I-ZnO based dye-sensitized solar cells (DSCs). Electrochemical impedance spectra demonstrate that ZnO CL pre-treatment and TiO2 PL post-treatment synergistically reduce charge-transfer resistance and suppress electron recombination. Furthermore, the electron lifetime in two combined modifications of IZnO + CL + PL photoelectrode is the longest in comparison with the other three photoelectrodes. As a consequence, the overall conversion efficiency of I-ZnO + CL + PL DSC is significantly enhanced to 6.79%, with a 36% enhancement compared with unmodified I-ZnO DSC. Moreover, the stability of I-ZnO + CL + PL cell is improved as compared to I-ZnO one. The mechanism of electron transfer and recombination upon the introduction of ZnO CL and TiO2 PL is also proposed in this work.