Electronic Structure and Optical Properties of Silicon Nanocrystals along their Aggregation Stages

The structural control of silicon nanocrystals is an important technological problem. Typically a distribution of nanocrystal sizes and shapes emerges under the uncontrolled aggregation of smaller clusters. The aim of this computational study is to investigate the evolution of the nanocrystal electronic states and their optical properties throughout their aggregation stages. To realistically tackle such systems, an atomistic electronic structure tool is required that can accommodate about tens of thousand nanocrystal and embedding lattice atoms with very irregular shapes. For this purpose, a computationally-efficient pseudopotential-based electronic structure tool is developed that can handle realistic nanostructures based on the expansion of the wavefunction of the aggregate in terms of bulk Bloch bands of the constituent semiconductors. With this tool, the evolution of the electronic states as well as the polarization-dependent absorption spectra correlated with the oscillator strengths over their aggregation stages are traced. The low-lying aggregate nanocrystal states develop binding and anti-binding counterparts of the isolated states. Such information may become instrumental with the maturity of the controlled aggregation of these nanocrystals.Comment: 5 pages, 7 figure

Alloying effects on the optical properties of Ge1−x_{1-x}Six_x nanocrystals from TDDFT and comparison with effective-medium theory

We present the optical spectra of Ge$_{1-x}$Si$_x$ alloy nanocrystals calculated with time-dependent density-functional theory in the adiabatic local-density ap proximation (TDLDA). The spectra change smoothly as a function of the compositio n $x$. On the Ge side of the composition range, the lowest excitations at the ab sorption edge are almost pure Kohn-Sham independent-particle HOMO-LUMO transitio ns, while for higher Si contents strong mixing of transitions is found. Within T DLDA the first peak is slightly higher in energy than in earlier independent-par ticle calculations. However, the absorption onset and in particular its composit ion dependence is similar to independent-particle results. Moreover, classical depolarization effects are responsible for a very strong suppression of the abs orption intensity. We show that they can be taken into account in a simpler way using Maxwell-Garnett classical effective-medium theory. Emission spectra are in vestigated by calculating the absorption of excited nanocrystals at their relaxe d geometry. The structural contribution to the Stokes shift is about 0.5 eV. Th e decomposition of the emission spectra in terms of independent-particle transit ions is similar to what is found for absorption. For the emission, very weak tra nsitions are found in Ge-rich clusters well below the strong absorption onset.Comment: submitted to Phys. Rev.

Is the largest aqueous gold cluster a superatom complex? Electronic structure & optical response of the structurally determined Au146(pMBA)57

The new water-soluble gold cluster Au146(pMBA)57, the structure of which has been recently determined at sub-atomic resolution by Vergara et al. [1], is the largest aqueous gold cluster ever structurally determined and likewise the smallest cluster with a stacking fault. The core presents a twinned truncated octahedron, while additional peripheral gold atoms follow a C2 rotational symmetry. According to the usual counting rules of the superatom complex (SAC) model, the compound attains a number of 92 SAC electrons if the overall net charge is 3- (three additional electrons). As this is the number of electrons required for a major shell closing, the question arises if Au146(pMBA)57 should be regarded as a superatom complex. Starting from the experimental coordinates we have analyzed the structure using density-functional theory. The optimized (relaxed) structure retains all the connectivity of the experimental coordinates, while removing much of its irregularities in interatomic distances, thereby enhancing the C2-symmetry feature. Analyzing the angular-momentum projected states, we show that, despite a small gap, the electronic structure does not exhibit SAC model character. In addition, optical absorption spectra are found to be relatively smooth compared to the example of the Au144(SR)60 cluster. The Au146(SR)57 cluster does not derive its stability from SAC character; it cannot be considered a superatom complex

High temperature structural and magnetic properties of cobalt nanowires

We present in this paper the structural and magnetic properties of high aspect ratio Co nanoparticles (~10) at high temperatures (up to 623 K) using in situ X ray diffraction (XRD) and SQUID characterizations. We show that the anisotropic shapes, the structural and texture properties are preserved up to 500 K. The coercivity can be modelled by u0Hc=2(Kmc+Kshape)/Ms with Kmc the magnetocrystalline anisotropy constant, Kshape the shape anisotropy constant and Ms the saturation magnetization. Hc decreases linearly when the temperature is increased due to the loss of the Co magnetocrystalline anisotropy contribution. At 500K, 50% of the room temperature coercivity is preserved corresponding to the shape anisotropy contribution only. We show that the coercivity drop is reversible in the range 300 - 500 K in good agreement with the absence of particle alteration. Above 525 K, the magnetic properties are irreversibly altered either by sintering or by oxidation.Comment: 8 pages, 7 figures, submitted to Journal of Solid State Chemistr

Optical spectra of silver clusters and nanoparticles of all sizes from the TDDFT+U method

The localized surface-plasmon resonances (LSPRs) of coinage-metal clusters and nanoparticles provide the basis for a great number of applications, the conception and necessary optimization of which require precise theoretical description and understanding. However, for the size range from clusters of a few atoms through nanoparticles of a few nanometers, where quantum effects and atomistic structure play a significant role, none of the methods employed to date has been able to provide high-quality spectra for all sizes. The main problem is the description of the filled shells of d electrons which influence the optical response decisively. In the present work we show that the DFT+U method, employed with real-time time-dependent density-functional theory calculations (RT-TDDFT), provides spectra in good agreement with experiment for silver clusters ranging from 4 to 923 atoms, the latter representing a nanoparticle with a diameter of 3 nm. Both the electron-hole-type discrete spectra of the smallest clusters and the broad plasmon resonances of the larger sizes are obtained. All calculations have been carried out using the same value of the effective U parameter that has been found to provide good results in bulk silver. The agreement with experiment for all sizes shows that the U parameter is surprisingly transferable. Our results open the pathway for TDDFT calculations of many practically relevant systems including clusters coupled to bio-molecules or to other nano-objects

Theoretical study of the insulating oxides and nitrides: SiO2, GeO2, Al2O3, Si3N4, and Ge3N4

An extensive theoretical study is performed for wide bandgap crystalline oxides and nitrides, namely, SiO_{2}, GeO_{2}, Al_{2}O_{3}, Si_{3}N_{4}, and Ge_{3}N_{4}. Their important polymorphs are considered which are for SiO_{2}: $\alpha$-quartz, $\alpha$- and $\beta$-cristobalite and stishovite, for GeO_{2}: $\alpha$-quartz, and rutile, for Al_{2}O_{3}: $\alpha$-phase, for Si_{3}N_{4} and Ge_{3}N_{4}: $\alpha$- and $\beta$-phases. This work constitutes a comprehensive account of both electronic structure and the elastic properties of these important insulating oxides and nitrides obtained with high accuracy based on density functional theory within the local density approximation. Two different norm-conserving \textit{ab initio} pseudopotentials have been tested which agree in all respects with the only exception arising for the elastic properties of rutile GeO_{2}. The agreement with experimental values, when available, are seen to be highly satisfactory. The uniformity and the well convergence of this approach enables an unbiased assessment of important physical parameters within each material and among different insulating oxide and nitrides. The computed static electric susceptibilities are observed to display a strong correlation with their mass densities. There is a marked discrepancy between the considered oxides and nitrides with the latter having sudden increase of density of states away from the respective band edges. This is expected to give rise to excessive carrier scattering which can practically preclude bulk impact ionization process in Si_{3}N_{4} and Ge_{3}N_{4}.Comment: Published version, 10 pages, 8 figure

Length and alpha-Fe content control of self-organised ferromagnetic nanowires encapsulated by multiwalled carbon nanotubes by low flow-rate CVD

Engineering and Physical Science Research Council, UK

Iron-filled multiwalled carbon nanotubes surface-functionalized with paramagnetic Gd (III): A candidate dual-functioning MRI contrast agent and magnetic hyperthermia structure

The authors are grateful for the financial support from the Engineering and Physical Science Research Council, UK

Anisotropy effects on the plasmonic response of nanoparticle dimers

We present an ab initio study of the anisotropy and atomic relaxation effects on the optical properties of nanoparticle dimers. Special emphasis is placed on the hybridization process of localized surface plasmons, plasmon-mediated photoinduced currents, and electric-field enhancement in the dimer junction. We show that there is a critical range of separations between the clusters (0.1–0.5 nm) in which the detailed atomic structure in the junction and the relative orientation of the nanoparticles have to be considered to obtain quantitative predictions for realistic nanoplasmonic devices. It is worth noting that this regime is characterized by the emergence of electron tunneling as a response to the driven electromagnetic field. The orientation of the particles not only modifies the attainable electric field enhancement but can lead to qualitative changes in the optical absorption spectrum of the system.We thankfully acknowledge financial support by the European Research Council (ERC-2010-AdG Proposal No. 267374 and ERC-2011-AdG Proposal No. 290891), the Spanish Government (Grants MAT2011-28581-C02-01, FIS2013-46159-C3-1-P, and MAT2014-53432-C5-5-R), and the Basque Country Government (Grupos Consolidados IT-578-13).Peer Reviewe