Role of local fields in the optical properties of silicon nanocrystals using the tight binding approach

The role of local fields in the optical response of silicon nanocrystals is analyzed using a tight binding approach. Our calculations show that, at variance with bulk silicon, local field effects dramatically modify the silicon nanocrystal optical response. An explanation is given in terms of surface electronic polarization and confirmed by the fair agreement between the tight binding results and that of a classical dielectric model. From such a comparison, it emerges that the classical model works not only for large but also for very small nanocrystals. Moreover, the dependence on size of the optical response is discussed, in particular treating the limit of large size nanocrystals.Comment: 4 pages, 4 figure

Effect of quantum confinement on the dielectric function of PbSe

Monolayers of lead selenide nanocrystals of a few nanometers in height have been made by electrodeposition on a Au(111) substrate. These layers show a thickness-dependent dielectric function, which was determined using spectroscopic ellipsometry. The experimental results are compared with electronic structure calculations of the imaginary part of the dielectric function of PbSe nanocrystals. We demonstrate that the size-dependent variation of the dielectric function is affected by quantum confinement at well-identifiable points in the Brillouin zone, different from the position of the band-gap transition

Dirac Cones, Topological Edge States, and Nontrivial Flat Bands in Two-Dimensional Semiconductors with a Honeycomb Nanogeometry

We study theoretically two-dimensional single-crystalline sheets of semiconductors that form a honeycomb lattice with a period below 10 nm. These systems could combine the usual semiconductor properties with Dirac bands. Using atomistic tight-binding calculations, we show that both the atomic lattice and the overall geometry influence the band structure, revealing materials with unusual electronic properties. In rocksalt Pb chalcogenides, the expected Dirac-type features are clouded by a complex band structure. However, in the case of zinc-blende Cd-chalcogenide semiconductors, the honeycomb nanogeometry leads to rich band structures, including, in the conduction band, Dirac cones at two distinct energies and nontrivial flat bands and, in the valence band, topological edge states. These edge states are present in several electronic gaps opened in the valence band by the spin-orbit coupling and the quantum confinement in the honeycomb geometry. The lowest Dirac conduction band has S-orbital character and is equivalent to the pi-pi* band of graphene but with renormalized couplings. The conduction bands higher in energy have no counterpart in graphene; they combine a Dirac cone and flat bands because of their P-orbital character. We show that the width of the Dirac bands varies between tens and hundreds of meV. These systems emerge as remarkable platforms for studying complex electronic phases starting from conventional semiconductors. Recent advancements in colloidal chemistry indicate that these materials can be synthesized from semiconductor nanocrystals.Comment: 12 pages, 12 figure

Frequency-dependent spontaneous emission rate from CdSe and CdTe nanocrystals: influence of dark states

We studied the rate of spontaneous emission from colloidal CdSe and CdTe nanocrystals at room temperature. The decay rate, obtained from luminescence decay curves, increases with the emission frequency in a supra-linear way. This dependence is explained by the thermal occupation of dark exciton states at room temperature, giving rise to a strong attenuation of the rate of emission. The supra-linear dependence is in agreement with the results of tight-binding calculations.Comment: 11 page

Topological states in multi-orbital HgTe honeycomb lattices

Research on graphene has revealed remarkable phenomena arising in the honeycomb lattice. However, the quantum spin Hall effect predicted at the K point could not be observed in graphene and other honeycomb structures of light elements due to an insufficiently strong spin-orbit coupling. Here we show theoretically that 2D honeycomb lattices of HgTe can combine the effects of the honeycomb geometry and strong spin-orbit coupling. The conduction bands, experimentally accessible via doping, can be described by a tight-binding lattice model as in graphene, but including multi-orbital degrees of freedom and spin-orbit coupling. This results in very large topological gaps (up to 35 meV) and a flattened band detached from the others. Owing to this flat band and the sizable Coulomb interaction, honeycomb structures of HgTe constitute a promising platform for the observation of a fractional Chern insulator or a fractional quantum spin Hall phase.Comment: includes supplementary materia

Interband, intraband and excited-state direct photon absorption of silicon and germanium nanocrystals embedded in a wide band-gap lattice

Embedded Si and Ge nanocrystals (NCs) in wide band-gap matrices are studied theoretically using an atomistic pseudopotential approach. From small clusters to large NCs containing on the order of several thousand atoms are considered. Effective band-gap values as a function of NC diameter reproduce very well the available experimental and theoretical data. It is observed that the highest occupied molecular orbital for both Si and Ge NCs and the lowest unoccupied molecular orbital for Si NCs display oscillations with respect to size among the different irreducible representations of the $C_{3v}$ point group to which these spherical NCs belong. Based on this electronic structure, first the interband absorption is thoroughly studied which shows the importance of surface polarization effects that significantly reduce the absorption when included. This reduction is found to increase with decreasing NC size or with increasing permittivity mismatch between the NC core and the host matrix. Reasonable agreement is observed with the experimental absorption spectra where available. The deformation of spherical NCs into prolate or oblate ellipsoids are seen to introduce no pronounced effects for the absorption spectra. Next, intraconduction and intravalence band absorption coefficients are obtained in the wavelength range from far-infrared to visible region. These results can be valuable for the infrared photodetection prospects of these NC arrays. Finally, excited-state absorption at three different optical pump wavelengths, 532 nm, 355 nm and 266 nm are studied for 3- and 4 nm-diameter NCs. This reveals strong absorption windows in the case of holes and a broad spectrum in the case of electrons which can especially be relevant for the discussions on achieving gain in these structures.Comment: Published version, 13 pages, 15 figures, local field effects include

Microplastic Pollution Focused on Sources, Distribution, Contaminant Interactions, Analytical Methods, and Wastewater Removal Strategies: A Review

Plastics have been one of the most useful materials in the world, due to their distinguishing characteristics: light weight, strength, flexibility, and good durability. In recent years, the growing consumption of plastics in industries and domestic applications has revealed a serious problem in plastic waste treatments. Pollution by microplastics has been recognized as a serious threat since it may contaminate all ecosystems, including oceans, terrestrial compartments, and the atmosphere. This micropollutant is spread in all types of environments and is serving as a “minor but efficient” vector for carrier contaminants such as pesticides, pharmaceuticals, metals, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The need to deeply study and update the evolution of microplastic sources, toxicology, extraction and analysis, and behavior is imperative. This review presents an actual state of microplastics, addressing their presence in the environment, the toxicological effects and the need to understand their extent, their interactions with toxic pollutants, the problems that arise in the definition of analytical methods, and the possible alternatives of treatmentsThis research was funded by the Associate Laboratory for Green Chemistry-LAQV, which received financial support from UIDB/50006/2020, UIDP/50006/2020, and LA/P/0008/2020 by the Fundação para a Ciência e a Tecnologia (FCT)/Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national funds. The research was funded also by FCT and BiodivRestore Joint Call 2020–2021—European Union’s Horizon 2020 research and innovation programme under grant agreement No 101003777-BiodivRestore-406/DivRestore/0002/2020-BioReset-“Biodiversity restoration and conservation of inland water ecosystems for environmental and human well-being”. Virgínia Cruz Fernandes thanks FCT for the financial support through a postdoctoral fellowship (SFRH/BPD/109153/2015). The authors are greatly indebted to all financing sourcesinfo:eu-repo/semantics/publishedVersio

Study of the Potential Accumulation of the Pesticide Alpha-Endosulfan by Microplastics in Water Systems

Microplastics (MP) are spread into all ecosystems and represent a threat to the equilibrium of the environment and human health, not only due to their intrinsic characteristics but also to their action as effective carriers of contaminants, such as pesticides, pharmaceuticals, polychlorinated biphenyls and polycyclic aromatic hydrocarbons. The pesticide α-endosulfan is persistent and spread in the environment. The MP are another possible way of dissemination to be considered in the fate of this pesticide. The adsorption dynamics of α-endosulfan by six different MP (low-density polyethylene—LDPE, polyethylene-co-vinyl acetate, unplasticized polyvinyl chloride, polyamide 6, polystyrene granule, polypropylene granule) with different sizes/shapes and chemical compositions were evaluated. The most critical situation was identified for the system LDPE (particle size < 300 μm). Equilibrium studies (48 h equilibrium time) were performed for distilled, tap and filtered river water. Based on the Langmuir model parameters, the highest maximum adsorption capacity was obtained for distilled water, followed by filtered river and tap waters (i.e., 366 ± 39, 247 ± 38, 157 ± 22 μg/g). The obtained results demonstrate the important role that microplastics may have in the fate and transport of pesticides and their potentially harmful effect on the environment, which requires further investigationThis research was funded by the Associate Laboratory for Green Chemistry-LAQV, which received financial support from UIDB/50006/2020, UIDP/50006/2020, and LA/P/0008/2020 by the Fundação para a Ciência e a Tecnologia (FCT)/Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national funds. This research was funded through the 2019–2020 Biodiversa & Water JPI joint call for research proposals, under the BiodivRestore ERA-Net COFUND programme, DivRestore/0002/2020, and with the funding organisation FCT, Portugal. Virgínia Cruz Fernandes thanks FCT for the financial support through a postdoctoral fellowship (SFRH/BPD/109153/2015). Also, Sílvia Daniela Martinho thanks FCT for the financial support through a doctoral fellowship (SFRH/BD/13595/2022). The authors are greatly indebted to all financing sources.info:eu-repo/semantics/publishedVersio

Agar extraction from integrated multitrophic aquacultured Gracilaria vermiculophylla: Evaluation of a microwave-assisted process using response surface methodology

Microwave-assisted extraction (MAE) of agar from Gracilaria vermiculophylla, produced in an integrated multitrophic aquaculture (IMTA) system, from Ria de Aveiro (northwestern Portugal), was tested and optimized using response surface methodology. The influence of the MAE operational parameters (extraction time, temperature, solvent volume and stirring speed) on the physical and chemical properties of agar (yield, gel strength, gelling and melting temperatures, as well as, sulphate and 3,6-anhydro-Lgalactose contents) was evaluated in a 2^4 orthogonal composite design. The quality of the extracted agar compared favorably with the attained using traditional extraction (2 h at 85ºC) while reducing drastically extraction time, solvent consumption and waste disposal requirements. Agar MAE optimum results were: an yield of 14.4 ± 0.4%, a gel strength of 1331 ± 51 g/cm2, 40.7 ± 0.2 _C gelling temperature, 93.1 ± 0.5ºC melting temperature, 1.73 ± 0.13% sulfate content and 39.4 ± 0.3% 3,6-anhydro-L-galactose content. Furthermore, this study suggests the feasibility of the exploitation of G. vermiculophylla grew in IMTA systems for agar production

Model for the on-site matrix elements of the tight-binding hamiltonian of a strained crystal: Application to silicon, germanium and their alloys

We discuss a model for the on-site matrix elements of the sp3d5s* tight-binding hamiltonian of a strained diamond or zinc-blende crystal or nanostructure. This model features on-site, off-diagonal couplings between the s, p and d orbitals, and is able to reproduce the effects of arbitrary strains on the band energies and effective masses in the full Brillouin zone. It introduces only a few additional parameters and is free from any ambiguities that might arise from the definition of the macroscopic strains as a function of the atomic positions. We apply this model to silicon, germanium and their alloys as an illustration. In particular, we make a detailed comparison of tight-binding and ab initio data on strained Si, Ge and SiGe.Comment: Submitted to Phys. Rev.