Band 9, Heft 2 - Topical Issue: Nanoscience and nanotechnology

This article contains a broad overview of etch process as one of the most important top-down technologies widely used in semiconductor manufacturing and surface modification of nanostructures. In plasma etching process, the complexity comes from the introduction of new materials and from the constant reduction in dimensions of the structures in microelectronics. The emphasis was made on two types of etching processes: dry etching and wet etching illustrated by three dimensional (3D) simulation results for the etching profile evolution based on the level set method. The etching of low-k dielectrics has been demonstrated via modelling the porous materials. Finally, simulation results for the roughness formation during isotropic etching of nanocomposite materials as well as smoothing of the homogeneous materials have also been shown and analyzed. Simulation results, presented here, indicate that with shrinking microelectronic devices, plasma and wet etching interpretative and predictive modeling and simulation have become increasingly more attractive as a tool for design, control and optimization of plasma reactors.

We review selected results concerning the interlayer exchange coupling in Fe/SixFe1−x , Fe/Ge and Co/Si layered structures. Among the ferromagnet/semiconductor systems, Fe/Si structures are the most popular owing to their strong antiferromagnetic interlayer coupling. We show that such interaction depends not only on semiconducting sublayer thickness, but also on deposition techniques and on the chemical composition of the sublayer as well. In similar heterostructures e.g. Fe/Ge, antiferromagnetic coupling was observed only in ion-beam deposited trilayers at low temperatures. In contrast, in Fe/Ge multilayers deposited by sputtering, no such coupling was found. However, when the Ge is partially substituted by Si, antiferromagnetic interlayer coupling appears. For Co/Si multilayers, we observed a very weak exchange coupling and its oscillatory behavior. The growth of Co on Si occurs in an island growth mode. The evolution of magnetic loop shapes can be successfully explained by the interplay between interlayer coupling and anisotropy terms.

We report on continuous-wave and time-resolved fluorescence spectroscopy studies of CdTe water-soluble nanocrystals at room temperature. For nanocrystals spread directly on the substrate we observe large variation both in fluorescence maximum energy and fluorescence lifetime. We attribute this to the influence of the surface of the nanocrystals on the stability of excitations in the nanocrystals. As the fluorescence lifetime of the nanocrystals is monitored, we find it increases with time from 6 to 18 ns and then saturates. Placing the nanocrystals in a polymer matrix remarkably improves the photostability and all the above-mentioned effects are diminished. Upon mixing the nanocrystals with gold spherical nanoparticles we observe a decrease of the fluorescence intensity due to efficient energy transfer to the nanoparticles.

We developed a fluorescence confocal microscope equipped with a hemispherical solid immersion lens (SIL) and apply it to study the optical properties of light-harvesting complexes. We demonstrate that the collection efficiency of the SIL-equipped microscope is significantly improved, as is the spatial resolution, which reaches 600 nm. This experimental setup is suitable for detailed studies of physical phenomena in hybrid nanostructures. In particular, we compare the results of fluorescence intensity measurements for a light-harvesting peridinin-chlorophyll-protein (PCP) complex with and without the SIL.

Atomic force microscopy (AFM) topographical studies and results of nanoindentation experiment for several palladium-carbon films (Pd-C film) deposited on various substrates and with varying palladium content are presented. Pd-C films were prepared by a physical vapor decomposition (PVD) process and next were modified by a chemical vapor decomposition (CVD) method to obtain carbonaceous porous structure with dispersed palladium nanograins and a variation in roughness. The dependence of film topography on the kind of substrate such as Al2O3, Mo polycrystalline foil and fused silica was studied by AFM. Nanomechanical properties such as hardness and the reduced indentation modulus were determined by nanoindentation. A comparison of these values for films with different Pd content deposited on various substrates is presented.

Polymer-nanostructured carbon composites (PNCC) using three different polymers as composite matrix materials (polyvinylacetate (PVAc), polyethylene glycol (PEG) and ethylene-vinylacetate copolymer (EVA)) have been developed. High structure carbon black Printex XE2 (Degussa AG) was used as a composites filler. Ethanol vapour sensor-effect of composites was determined as a change of electrical resistance as the composite was held in ethanol vapour for 30 seconds. Reversibility of electrical resistance of PNCC, response stability and repeatability have been measured and compared. The electrical resistance response of EVA-nanostructured carbon composite (EVA-NCC) to ethanol vapour as a function of vinylacetate content in the copolymer has been evaluated. Promising ethanol vapour sensor-effect has been observed for PEG-NCC followed by PVAc-NCC and EVA-NCC.

Electrical and optical properties of TiO2:Pd thin films deposited from Ti-Pd mosaic targets sputtered in reactive oxygen plasma have been studied. The properties were investigated for thin films with the Pd amount of 5.5 at. %, 8.4 at. % and 23 at. %. Based on resistivity measurements a drop from 103 down to almost 10−3Ωcm has been recorded when the Pd amount was varied from 5.5 at. % to 23 at. %, respectively. Moreover, it was shown that doping with different amounts of Pd results in the possibility of obtaining both types of electrical conduction: n-type for the TiO2 with 5.5 at. % and 8.4 at. % of Pd and p-type for the TiO2 with 23 at. % of Pd thin films. From optical measurements it has been found that as the Pd amount was increased the transmission through the thin films was reduced and position of the fundamental absorption edge was shifted toward a longer wavelength range of up to 600 nm. The optical band gap was calculated for direct and indirect transitions from optical absorption spectra. Structural properties were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The XRD patterns displayed occurrence of the crystalline, TiO2-rutile for lower Pd amounts (5.5 at. %, 8.4 at. %), while the TiO2:Pd (23 at. %) thin films displayed XRD-amorphous behaviour. Images obtained from AFM displayed dense, nanocrystalline structure with homogenous distribution of crystallites. Additionally performed secondary ion mass spectroscopy investigation confirmed homogenous distribution of Pd in the whole thickness of the prepared thin films.

Atomic layer deposition of HfO2 on unmodified graphene from HfCl4 and H2O was investigated. Surface RMS roughness down to 0.5 nm was obtained for amorphous, 30 nm thick hafnia film grown at 180°C. HfO2 was also deposited in a two-step temperature process where the initial growth of about 1 nm at 170°C was continued up to 10–30 nm at 300°C. This process yielded uniform, monoclinic HfO2 films with RMS roughness of 1.7 nm for 10–12 nm thick films and 2.5 nm for 30 nm thick films. Raman spectroscopy studies revealed that the deposition process caused compressive biaxial strain in graphene, whereas no extra defects were generated. An 11 nm thick HfO2 film deposited onto bilayer graphene reduced the electron mobility by less than 10% at the Dirac point and by 30–40% far away from it.

This work presents the application of the free solution electrophoresis method (FSE) in the metallic / semiconductive (M/S) separation process of the surfactant functionalized single-walled carbon nanotubes (SWCNTs). The SWCNTs synthesized via laser ablation were purified through high vacuum annealing and subsequent refluxing processes in aqua regia solution. The purified and annealed material was divided into six batches. First three batches were dispersed in anionic surfactants: sodium dodecyl sulfate (SDS), sodium cholate (SC) and sodium deoxycholate (DOC). The next three batches were dispersed in cationic surfactants: cetrimonium bromide (CTAB), benzalkonium chloride (BKC) and cetylpyridinium chloride (CPC). All the prepared SWCNTs samples were subjected to FSE separation process. The fractionated samples were recovered from control and electrode areas and annealed in order to remove the adsorbed surfactants on carbon nanotubes (CNTs) surface. The changes of the van Hove singularities (vHS) present in SWCNTs spectra were investigated via UV-Vis-NIR optical absorption spectroscopy (OAS).

The work presents the results of the scanning electron microscopy (SEM) and Raman spectrometry studies of carbonaceous nanostructures containing nickel nanocrystallites. The films were obtained using a two-step method. In the first phase the Physical Vapour Deposition (PVD) method was applied, whereas in the second Chemical Vapour Deposition (CVD) method was used. The paper presents results for samples with various Ni content obtained with different parameters of the two-phase technological process. The research confirms that the thin films obtained by PVD method contain Ni nanocrystallites distributed in a carbonaceous matrix. The matrix is composed of various carbon allotropes (amorphous carbon, graphite, fullerene). The thin films made by CVD method make a matrix when multiwalled, carbonaceous nanotubes are obtained. Depending on the technological process parameters of each phase, we obtain multiwall nanotubes with a various degree of defects.

The InAs quantum structures were formed in silicon by sequential ion implantation and subsequent thermal annealing. Two kinds of crystalline InAs nanostructures were successfully synthesized: nanodots (NDs) and nanopyramids (NPs). The peaks at 215 and 235 cm−1, corresponding to the transverse optical (TO) and longitudinal optical (LO) InAs single-phonon modes, respectively, are clearly visible in the Raman spectra. Moreover, the PL band at around 1.3 µm, due to light emission from InAs NDs with an average diameter 7±2 nm, was observed. The InAs NPs were found only in samples annealed for 20 ms at temperatures ranging from 1000 up to 1200°C. The crystallinity and pyramidal shape of InAs quantum structures were confirmed by HRTEM and XRD techniques. The average size of the NPs is 50 nm base and 50 nm height, and they are oriented parallel to the Si (001) planes. The lattice parameter of the NPs increases from 6.051 to 6.055 Å with the annealing temperature increasing from 1100 to 1200°C, due to lattice relaxation. Energy dispersive spectroscopy (EDS) shows almost stoichiometric composition of the InAs NPs.

Carbon nanotubes films have been studied with SEM and TEM. The studied films were obtained using a two step method: PVD process and CVD process. Strongly defected and curled carbon nanotubes containing Ni nanoparticles formed the film with thickness of about 300–400 nm. Observed carbon nanotubes were of lengths from 100 nm to 300 nm and did not stick to each other.

In this work, the influence of Tb-doping on structure, and especially hardness of nanocrystalline TiO2 thin films, has been described. Thin films were formed by a high-energy reactive magnetron sputtering process in a pure oxygen atmosphere. Undoped TiO2-matrix and TiO2:Tb (2 at. % and 2.6 at. %) thin films, had rutile structure with crystallite sizes below 10 nm. The high-energy process produces nanocrystalline, homogenous films with a dense and close packed structure, that were confirmed by X-ray diffraction patterns and micrographs from a scanning electron microscope. Investigation of thin film hardness was performed with the aid of a nanoindentation technique. Results of measurements have shown that the hardness of all manufactured nanocrystalline films is above 10 GPa. In the case of undoped TiO2 matrix, the highest hardness value was obtained (14.3 GPa), while doping with terbium results in hardness decreasing down to 12.7 GPa and 10.8 GPa for TiO2:(2 at. % Tb) and TiO2:(2.6 at. % Tb) thin films, respectively. Incorporation of terbium into TiO2-matrix also allows modification of the elastic properties of the films.

In this work photocatalytic properties of TiO2 thin films doped with different amount of Tb have been described. Thin films were prepared by high energy reactive magnetron sputtering process. Comparable photocatalytic activity has been found for all doped TiO2 thin films, while different amounts of Tb dopant (0.4 and 2.6 at. %) results in either an anatase or rutile structure. It was found that the terbium dopant incorporated into TiO2 was also responsible for the amount of hydroxyl groups and water particles adsorbed on the thin film surfaces and thus photocatalytic activity was few times higher in comparison with results collected for undoped TiO2 thin films.

The organization of magnetic materials into one-dimensional micro- and nanowires on designed media is discussed, exemplified by two experiments on the microscale and nanoscale, with regard to particles as basic building blocks for the growth and development of matter. In the first organizational experiments, cobalt (Co) micro-particles are assembled on patterned media with perpendicular magnetization by acoustic vibrations onto designed shapes reflecting macroscopically the parent material. In the second experiments, semiconductor Germanium-Dysprosium (Ge98Dy2) matter is assembled on gold (Au) catalytic nuclei in a tube reactor by physical vapor transport as clusters of nanowires. The underlying mechanisms of organization are described, and similarities and distinctive features in the processes are discussed. The role of the energy-input in the form of mechanical vibrations and heat is outlined with its similar impact on the assembly and growth of matter on surfaces. The description of these experiments in view of organization allows more control over the processes of planned arrangement on designed media. Routes for further progress in this direction are briefly outlined.

This contribution reports on charge and spin transport through graphene nanoribbons (GrNs) and carbon nanotubes (CNTs). The paper focuses on the giant magnetoresistance effect in these materials, and their potential usefulness for spintronic applications. As examples, the following devices are shortly discussed: GrNs in the ballistic transport regime, a CNT-based Schottky-barrier field effect transistor (CNT SB-FET), as well as CNT quantum dots in the Coulomb blockade limit.

The measurement of the surface topography in dynamic mode (intermittent contact mode) is one of the most popular ways of imaging surfaces at nanoscale with atomic force microscopy. It also allows obtaining so called phase images which reveal the viscous-elastic non-homogeneities of the surface, therefore can be used for detecting the presence of different materials. It is, however, very difficult to interpret the phase map due to the origin of phenomena, method of signal detection and processing. Therefore one cannot determine whether the observed feature is caused by increase or decrease of any of specific mechanical properties of the surface. In this article we present the modified setup of commercially available AFM, where detection of torsional oscillation of the cantilever is used for the determination of mechanical properties such as: elasticity, adhesion, peak force and energy dissipation. By advanced signal processing, the reconstruction of the force spectroscopy curve and the calculation of mentioned parameters are performed. All the operations are done in real time regime. The developed method allows one to obtain much more complex information about measured surface. Test measurement results are also presented.

Pilot studies concerning industrial scale application of post copper slag as a nano-additive for the modification of the corrosion resistance of cement composites have been described. The influence of a tribochemical treatment on some physicochemical properties as well as the corrosion resistance of the obtained composites have been evaluated based on DTG, RTG, and SEM coupled with EDX measurements and chemical analysis. It was observed that the so-called “size particle additive effect” influences the course and rate of transformations in the formed cement composites, and may lead to specific and desirable properties.

In this paper experimental results obtained by both 75As NQR and EPR spectroscopy are presented for the three-component system As-Sb-Se. The 75As NQR spectra of glasses of structures (As2Se3)0.78 (Sb2Se3)0.22, (As2Se3)0.75 (Sb2Se3)0.25, (As2Se3)0.5 (Sb2Se3)0.5 have broad lines with two Sb-NQR lines (corresponding to the Sb2Se3 units) and two 75As-NQR lines (corresponding to the As2Se3 units). Differences in the EPR spectra of the different glasses arise because of the different amounts of arsenic and antimony in their structure.

In the paper results of investigation of the influence of low concentration hydrogen on stress changes in thin catalytic metal films were discussed. The concentration of H2 was altered from 6 ppm to 1% of hydrogen (6N) in nitrogen (6N). Silicon beams covered with palladium or platinum films of various thicknesses were anchored at one end and their deflection at the other end was measured by atomic force microscope. Stress changes were determined by application of modified Stoney formula and compared with results of computer modelling. The influence of stress caused by hydrogen absorption on the alteration of output characteristics of AIII-N based hydrogen sensors was excluded. The time dependence of stress in metallic films for various hydrogen concentrations indicated dissociation limited mechanism of hydrogen absorption.

In this paper, a study of the influence of hydrogen (concentrations 6 ppm − 1%) on the work function of thin metallic films at moderately elevated temperatures is presented. The work function was measured indirectly by the observation of the surface potential of dedicated test structures using scanning surface potential microscope. Metallic layers with thicknesses of 10, 20, 30, and 50 nm were deposited on semiconductor substrates as well as on a thick gold layer. The investigations were focused on palladium thin films although a comparison to results obtained for platinum layers was also discussed.

The lithography is a basic microelectronic process which determines properties of fabricated device. The resolution of optical lithography applied nowadays is insufficient for creating high resolution patterns such as gate electrode in transistors. The scaling ability is the major motivation for undertaking experiments to elaborate high resolution lithography techniques. The atomic force microscope (AFM) is commonly used as tool for creation patterns in sub-micrometers resolution. In this paper, the results of simulations of electromagnetic field behavior during passing the gap with a size smaller than the wavelength of the optical lithography light source are presented. Also results of the nanoscratching lithography prepared for various parameters of force that are applied to the tip are summarized.

The influence of alcohol additives on etch rate anisotropy of Si(hkl) planes has been studied. The etching processes were carried out in 3 and 5 M KOH aqueous solutions saturated and non-saturated with alcohols. Isopropanol, 1-propanol and tert-butanol were examined. It has been showed that the etching process cannot be controlled only by the surface tension of the solution. Saturation of the etching solution with alcohols modifies etch rate anisotropy, lowering the ratio of the etch rate of (110) and vicinal planes to the etch rate of (100) plane. The morphology of Si(hkl) planes etched in 3 M KOH solution saturated with tert-butyl alcohol has been studied in detail. Smooth (331) and (221) planes have been achieved in this solution. The (100) plane turned out to be densely covered by hillocks, opposite to the (100) plane etched in weak-alkaline solution saturated with isopropanol. To explain this phenomenon, the mechanism of hillocks formation on Si(100) surface has been proposed.

In this work, the results of investigations of manufacturing ceramic materials on the basis of Ti, B, C and N containing systems are presented. The nanocrystalline ceramics were synthesized using a non-hydrolytic sol-gel method. The process was carried out in two stages. In the first low-temperature stage the precursor was obtained. The synthesis of ceramic phases, however, was conducted in the second high-temperature stage, in an argon atmosphere. Depending on the initial composition of the mixtures, the temperature and the time, the following products were obtained: TiCx, TiCxN1−x, TiB2 and B4C. The course of the process was investigated by thermogravimetric and differential scanning calorimetry methods (TG-DSC) coupled with mass spectrometry (MS). The solid state products were identified with use of X-ray diffraction (XRD). The size of the crystallites was estimated by the Scherrer method. The structure and morphology images of nanocrystalline powders were obtained using scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Transmission electron microscopy methods were used to determine the impact of two different implantation processes on the morphology of platinum silicide layers constituting low Schottky barrier contacts intended as the source/drain in MOS transistors. These processes are very promising candidates for the reduction of the Schottky barrier height (SBH) of contacts and are realized by (i) implantation-through-metal (ITM) followed by dopant-segregation induced by silicidation annealing and (ii) implantation-through-silicide (ITS) followed by dopant-segregation due to the post-silicidation annealing. The studies showed that depending on the type and conditions of the process (ITM or ITS with various post-silicidation annealing temperatures) different morphologies of PtSi layers and PtSi/Si interfaces roughnesses are observed. Better quality silicide layers and silicide/silicon interfaces were found for samples after the ITS process with post-silicidation annealing at 500°C than for samples after the ITM process or the ITS process with post-silicidation annealing at temperatures not exceeding 400°C. The observed microstructure of grains and interfaces in these samples, along with the impact of the dopant-segregation, may significantly influence the SBH value. The diffraction patterns and EDXS measurements revealed that regardless of the process type, the formed silicide layer is always PtSi.

We investigate light emission from ZnTe-based microcavities containing CdTe quantum dots (QDs), with 2D (planar cavity) and 0D (pillar cavities) photonic confinement. The angular distribution from the planar cavity is presented as well as 2D cross-sections of the far field distribution of radiation from the micropillars. The efficient and desirable modification of the isotropic radiation of the QDs is shown for such structures. The diffraction observed is found to be inherent for such experiments with large numerical aperture of the lens and small diameters of the investigated pillars. This diffraction is successfully modeled.

The photoluminescence spectra and luminescence excitation spectra of pure microcrystalline and nano-sized ZnWO4 as well as the ZnxNi1−x WO4 solid solutions were studied using vacuum ultraviolet (VUV) synchrotron radiation. The samples were also characterized by x-ray powder diffraction. We found that: (i) the shape of the photoluminescence band at 2.5 eV, being due to radiative electron transitions within the [WO6]6− anions, becomes modulated by the optical absorption of Ni2+ ions in the ZnxNi1−x WO4 solid solutions; and (ii) no significant change in the excitation spectra of Zn0.9Ni0.1WO4 is observed compared to pure ZnWO4. At the same time, a shift of the excitonic bands to smaller energies and a set of peaks, attributed to the one-electron transitions from the top of the valence band to quasi-localized states, were observed in the excitation spectrum of nano-sized ZnWO4.

We report construction of a model of polar nanoregions in the PMN relaxor ferroelectric based on first-principles lattice dynamics for chemically ordered supercells [S.A. Prosandeev et al., Phys. Rev. B 70, 134110 (2004)], combined with invariance under permutations and dipole-dipole interaction as a source supporting randomly oriented residual polarization. Representative analytical estimates of polar nanore-gion — supercell mapping reproduce both nonzero local and zero macroscopic polarization of the structure, as well as the temperature change of the supercell anisotropy at cooling and field cooling.

Polytype instability of SiC epitaxial films was the main focus of attention in the experiment performed since this factor has a decisive influence on graphene growth, which was the second stage of the experiment. Layers deposited in various initial C/Si ratios were analyzed. Our observations indicate that the initial C/Si ratio in epitaxial growth is a crucial parameter determining which polytype will be grown, in particular for cubic (3C) or hexagonal (4H) polytypes. If the initial C/Si ratio was close to its final value, the dominant polytype was 4H. On the other hand, when the initial C/Si ratio was close to zero, 3C became the major polytype in spite of a non favourable growth temperature. The results for graphene growth on an epi-SiC layer and a bulk substrate, in which case the dominant polytype was 4H, are also presented. These results indicate that layers on epitaxial 4H-SiC are thicker, more relaxed and have better quality in comparison with samples on 4H-SiC substrates. Morphology and defects in SiC epilayers were analyzed using Nomarsky optical microscopy, scanning electron microscopy (SEM) and high resolution X-ray diffraction (XRD). Graphene quality was characterized by Raman spectroscopy.

Molecular dynamics simulations are carried out to investigate the manipulation of metallic clusters on stepped surfaces. Five surface forms are considered in the simulations. The system parts are made of pure transition metals and Sutton-Chen many-body potential is used as interatomic potential. The conditions which are subjected to change in the tests include: materials used for particles and substrate, and surface step conditions. In addition to qualitative observations, two criteria which represent the particle deformation and substrate abrasion are utilized as evaluation tools and are computed for each case. Simulation results show the effect of the aforementioned working conditions on the particle behavior as well as changes in the pushing forces. Obtaining this sort of knowledge is highly beneficial for further experiments in order to be able to plan the conditions and routines which guarantee better success in the manipulation process.

The relaxation processes and the properties of polymer/ceramic nanocomposites have been studied by the 1H nuclear magnetic resonance methods. Nanocomposites of poly(ethylene terephthalate) PET and poly(phenylene sulfide) PPS with 0.25, 2.5 and 5% wt. barium titanate BT were prepared using a twin screw extruder and injection moulding machine. The spin-lattice relaxation time T1, second moment M2 and the motional parameters as e.g. the activation energies in the nanocomposites were investigated.

In order to investigate the specifications of nanoscale transistors, we have used a three dimensional (3D) quantum mechanical approach to simulate square cross section silicon nanowire (SNW) MOSFETs. A three dimensional simulation of silicon nanowire MOSFET based on self consistent solution of Poisson-Schrödinger equations is implemented. The quantum mechanical transport model of this work uses the non-equilibrium Green’s function (NEGF) formalism. First, we simulate a double-gate (DG) silicon nanowire MOSFET and compare the results with those obtained from nanoMOS simulation. We understand that when the transverse dimension of a DG nanowire is reduced to a few nanometers, quantum confinement in that direction becomes important and 3D Schrödinger equation must be solved. Second, we simulate gate-all-around (GAA) silicon nanowire MOSFETs with different shapes of gate. We have investigated GAA-SNW-MOSFET with an octagonal gate around the wire and found out it is more suitable than a conventional GAA MOSFET for its more I on/I off, less Drain-Induced-Barrier-Lowering (DIBL) and less subthreshold slope.

Caddisfly (Trichopera) can glue diverse material underwater with a silk fiber. This makes it a particularly interesting subject for biomimetcs. Better understanding of silk composition and structure could lead to an adhesive capable to close bleeding wounds or to new biomaterials. However, while spiderweb or silkworm secretion is well researched, caddisfly silk is still poorly understood. Here we report a first nanomechanical analysis of H. Angustipennis caddisfly silk fiber. An Atomic Force Microscope (AFM) imaging shows dense 150 nm bumps on silk surface, which can be identified as one of features responsible for its outstanding adhesive properties. AFM force spectroscopy at the fiber surface showed, among others, characteristic saw like pattern. This pattern is attributed to sacrificial bond stretching and enhances energy dissipation in mechanical deformation. Similarities of some force curves observed on Tegenaria domestica spiderweb and caddisfly silk are also discussed. Steered Molecular Dynamics simulations revealed that the strength of short components of Fib-H HA species molecules, abundant in Trichoptera silk is critically dependent on calcium presence.

The formalism of line symmetry groups for one-periodic (1D) nanostructures with rotohelical symmetry has been applied for symmetry analysis of single-walled titania nanotubes (SW TiO2 NTs) formed by rolling up the stoichiometric two-periodic (2D) slabs of anatase structure. Either six- or twelve-layer (101) slabs have been cut from TiO2 crystal in a stable anatase phase. After structural optimization, the latter keeps the centered rectangular symmetry of initial slab slightly compressed along a direction coincided with large sides of elemental rectangles. We have considered two sets of SW TiO2 NTs with optimized six- and twelve-layer structures, which possess chiralities (−n, n) and (n, n) of anatase nanotubes. To analyze the structural and electronic properties of titania slabs and nanotubes, we have performed their ab initio LCAO calculations, using the hybrid Hartree-Fock/Kohn-Sham exchange-correlation functional PBE0. The band gaps (Δɛ gap) and strain energies (E strain) of six-layer nanotubes have been computed and analyzed as functions of NT diameter (D NT). As to models of 12-layer SW TiO2 NTs of both chiralities, their optimization results in structural exfoliation, i.e., the multi-walled structure should be rather formed in nanotubes with such a number of atomic layers.

The electronic, structural and phonon properties of antiferromagnetic wolframite-type NiWO4 have been studied using first-principles spin-polarized LCAO calculations based on the hybrid Hartree-Fock (HF)/density functional (DFT) scheme. The influence of different percentages of HF contribution, i.e. different correlation strength, on the structure and phonon frequencies has been investigated and compared with the available experimental data.

ZnWO4 powders with grain size in range 20 nm–10 µm have been synthesized by a simple combustion method and subsequent calcinations. The photocatalytic activities of powders were tested by degradation of methylene blue solution under UV light. The luminescence spectra and luminescence decay kinetics were studied and luminescence decay time dependence on average powder-grain size was obtained. The correlation between self-trapped exciton luminescence decay time and photocatalytic activity of ZnWO4 powders was shown. A model explaining the excitonic luminescence decay time correlation with photocatalytic activity was proposed.

The results of ab initio slab calculations of surface relaxations, rumplings and charge distribution for the different terminations of the MgF2 (011) and (111) polar surfaces are presented and discussed. We have employed the computer code CRYSTAL with the Gaussian basis set and the hybrid B3PW exchange-correlation functional. Despite the ionic nature of the chemical bonding at both surfaces, a considerable decrease of the optical band gap is predicted (1.3 eV or 10%) for the (111) surface as compared to the bulk.

This theoretical study focuses on junctions between the carbon nanotubes (CNTs) and contacting metallic elements of a nanocircuit. Numerical simulations on the conductance and resistance of these contacts have been performed using the multiple scattering theory and the effective media cluster approach. Two models for CNT-metal contacts have been considered in this paper: a) first principles “liquid metal” model and b) semi-empirical model of “effective bonds” based on Landauer notions on ballistic conductivity. Within the latter, which is a more adequate description of chirality effects, we have simulated both single-wall (SW) and multi-wall (MW) CNTs with different morphology. Results of calculations on resistance for different CNT-Me contacts look quantitatively realistic (from several to hundreds kOhm, depending on chirality, diameter and thickness of MW CNT). The inter-wall transparency coefficient for MW CNT has been also simulated, as an indicator of possible ‘radial current’ losses.

In the current study, we have performed ab initio DFT calculations on the gradually growing 2D periodic models of capped single-wall carbon nanotubes (SW CNTs) upon their perpendicular junctions with the Ni(111) substrate, in order to understand the peculiarities of the initial stage of their growth on either smooth or nanostructured catalytic particles. Appearance of the adsorbed carbon atoms upon the substrate follows from the dissociation of CVD hydrocarbon molecules, e.g., CH4: (CH4)ads → (CH)ads+3Hads and (CH)ads → Cads+Hads. (Since the effective growth of CNTs upon Ni nanoparticles occur inside the nanopores of amorphous alumina, we have also simulated analogous surface reactions upon the θ-Al2O3(010) slabs). Association of the adsorbed carbon atoms upon the catalyst surface precedes further swelling of the (Cn)ads islands after appearance of pentagonal defects within a honeycomb sheet which are more probable upon the catalyst surface containing either defects or nanoclusters (as in the case of the nanostructured substrate). The gradual growth of the capped CNTs is considerably more effective upon the nanostructured Ni(111) substrate compared to a smooth nickel substrate (cf. values of CNT adhesion energy per boundary C atom for chiralities of either armchair-type, 4.04 vs. 2.51 eV, or zigzag-type, 4.61 vs. 2.14 eV, respectively). The electronic charge transfer from the Ni catalyst towards the CNTs has been calculated for both chiralities (> 1 e per C atom), i.e., quite strong chemical bonds are formed within the CNT/Ni(111) interconnects.

Composite material based on a TiO2 matrix doped with Sm3+ ions and co-doped with silver was investigated. Samarium ions together with nano- and micro-aggregates of silver were incorporated into the titanium alkoxide during the sol-gel process. Samarium ions were excited either directly (λ exc = 488 nm) or through the TiO2 host (λ exc = 355 nm). It was revealed that samarium fluorescence (λ exc = 488 nm) in gelled TiO2 films is enhanced by up to 20 times in the vicinity of silver inclusions. Sensitizing and plasmonic mechanisms of enhancement in Sm3+ fluorescence are discussed.

Light polarization effects on a holographic grating recording in a glassy chalcogenide a-As40S15Se45 film has been experimentally studied and compared with previously studied glassy molecular azobenzene film 8a at 633, using s − s,p − p, CE-1 and CE-2 circular-elliptic recording-beam polarizations (differing by light electric field rotation directions). The azocompound exhibited much higher self-diffraction efficiency (SDE) and diffraction efficiency whereas chalcogenide was more sensitive. Their recording efficiency polarization dependences also were different. SDE up to 45% was achieved in 8a with p − p and up to 2.6% in a-As40S15Se45 with CE-2 polarized recording beams. The polarization changes in the diffraction process were studied as well in these and other materials (11, 16, 19 and a-As2S3 film, LiTaO3:Fe crystal). It was found that light polarization changes in the process of diffraction from gratings recorded vectorially by s−p polarizations depended on chemical composition, wavelength, and exposure time. Vector gratings with SDE up to 25% were recorded in 8a, rotating a linear polarization by 90°. No light polarization changes were found in azobenzene 19 and chalcogenide films and in LiTaO3:Fe crystal, thus showing a vector recording of scalar holograms. The recording mechanisms in azocompounds and chalcogenides are discussed and compared.

Hydrated pastes of ordinary Portland cement prepared with different water-to-cement ratios were investigated by using the small-angle neutron scattering technique in the region of Q ∈ (0.0045, 0.11) Å−1. Samples of cement pastes were subjected to non-standard hydration conditions using a mix with D2O, low RH, and water-to-cement ratios spread over a very wide interval (0.4; 1.4). The investigation was focused on testing the structural stability of nano-metric particles in the cement C-S-H gel. Owing to the high structural stability of these nano-particles, their average diameter might be used as a microscopic parameter characterizing the nano-metric structure of C-S-H gels. The average diameter of the nano-particles of the studied ordinary Portland cement CEMI 42.5 R-SC was found to be close to the value of 4.2 nm and independent of the water-to-cement ratios.

In this paper we report structural, magnetic and transport properties of strongly textured Ni51Mn36Sn13 thin films. The off-stoichiometric Heusler alloy films with 200 nm thickness were sputter-deposited on a MgO(100) substrate at 500 K and after annealed at 1000 K in UHV conditions. The textured growth was confirmed by x-ray diffraction in Bragg-Brentano geometry. The temperature dependence of the magnetic properties was measured by VSM and FMR methods. The electron transport measurements were carried out in function of temperature in 0 Oe and 50 kOe fields. All measurements corroborate the existence of the martensitic transformation in the film. Furthermore, transport measurements reveal an influence of the magnetic field on the transition temperature.

In this work we study the influence of plasmon excitations on the excitation dynamics within a protein complex embedding two chlorophyll molecules coupled to a gold nanosphere. Small separation between the chlorophylls and metallic nanoparticle allows us to simplify the calculations of the Förster energy transfer rate and non-radiative processes by replacing a spherical nanoparticle with a metallic surface. Our results show modifications of all relevant processes and the energy transfer pathways within the system as well as the radiative processes. Plasmon induced changes result in strong qualitative effects of the fluorescence of the studied light-harvesting complex.

A novel polymerizable surfactant (so-called surfmer) was synthesized and characterized according to its structure, surface activity and polymerization ability. Polymeric micelles (size of 6 and 130 nm) appeared in the polyreaction initiated by free radicals from VA-044. In the presence of the monomer (i.e., methyl methacrylate) microemulsion systems were formed that in turn were transformed into latex entities (size — 40 nm). Additionally, an emulsion polymerization was performed with the use of n-hexadecane as an oil phase resulting in the production of nanocapsules (size in the range — 165–220 nm). The shape and morphologies of the nanoobjects were confirmed using Atomic Force Microscopy (AFM).