Hierarchical Surface Structures and Large-Area Nanoscale Gratings in As2S3 and As2Se3 Films Irradiated with Femtosecond Laser Pulses.

Chalcogenide vitreous semiconductors (ChVSs) find application in rewritable optical memory storage and optically switchable infrared photonic devices due to the possibility of fast and reversible phase transitions, as well as high refractive index and transmission in the near- and mid-infrared spectral range. Formed on such materials, laser-induced periodic surface structures (LIPSSs), open wide prospects for increasing information storage capacity and create polarization-sensitive optical elements of infrared photonics. In the present work, a possibility to produce LIPSSs under femtosecond laser irradiation (pulse duration 300 fs, wavelength 515 nm, repetition rate up to 2 kHz, pulse energy ranged 0.03 to 0.5 µJ) is demonstrated on a large (up to 5 × 5 mm2) area of arsenic sulfide (As2S3) and arsenic selenide (As2Se3) ChVS films. Scanning electron and atomic force microscopy revealed that LIPSSs with various periods (170-490 nm) and orientations can coexist within the same irradiated region as a hierarchical structure, resulting from the interference of various plasmon polariton modes generated under intense photoexcitation of nonequilibrium carriers within the film. The depth of the structures varied from 30 to 100 nm. The periods and orientations of the formed LIPSSs were numerically simulated using the Sipe-Drude approach. A good agreement of the calculations with the experimental data was achieved.

Neurotoxicity of Silver Nanoparticles and Non-Linear Development of Adaptive Homeostasis with Age.

For the first time in the world, the behavioral functions of laboratory mammals exposed to silver nanoparticles were studied with regard to age. Silver nanoparticles coated with polyvinylpyrrolidone with a size of 8.7 nm were used in the present research as a potential xenobiotic. Elder mice adapted to the xenobiotic better than the younger animals. Younger animals demonstrated more drastic anxiety than the elder ones. A hormetic effect of the xenobiotic in elder animals was observed. Thus, it is concluded that adaptive homeostasis non-linearly changes with age increase. Presumably, it may improve during the prime of life and start to decline just after a certain stage. This work demonstrates that age growth is not directly conjugated with the organism fading and pathology development. Oppositely, vitality and resistance to xenobiotics may even improve with age at least until the prime of life.

Femtosecond Laser Fabrication of Anisotropic Structures in Phosphorus- and Boron-Doped Amorphous Silicon Films.

Femtosecond laser-modified amorphous silicon (a-Si) films with optical and electrical anisotropy have perspective polarization-sensitive applications in optics, photovoltaics, and sensors. We demonstrate the formation of one-dimensional femtosecond laser-induced periodic surface structures (LIPSS) on the surface of phosphorus- (n-a-Si) and boron-doped (p-a-Si) amorphous silicon films. The LIPSS are orthogonal to the laser polarization, and their period decreases from 1.1 ± 0.1 µm to 0.84 ± 0.07 µm for p-a-Si and from 1.06 ± 0.03 to 0.98 ± 0.01 for n-a-Si when the number of laser pulses per unit area increases from 30 to 120. Raman spectra analysis indicates nonuniform nanocrystallization of the irradiated films, with the nanocrystalline Si phase volume fraction decreasing with depth from ~80 to ~40% for p-a-Si and from ~20 to ~10% for n-a-Si. LIPSS' depolarizing effect, excessive ablation of the film between LIPSS ridges, as well as anisotropic crystalline phase distribution within the film lead to the emergence of conductivity anisotropy of up to 1 order for irradiated films. Current-voltage characteristic nonlinearity observed for modified p-a-Si samples may be associated with the presence of both the crystalline and amorphous phases, resulting in the formation of potential barriers for the in-plane carrier transport and Schottky barriers at the electric contacts.

Artificial Anisotropy in Ge2Sb2Te5 Thin Films after Femtosecond Laser Irradiation.

Ge2Sb2Te5 (GST225) looks to be a promising material for rewritable memory devices due to its relatively easy processing and high optical and electrophysical contrast for the crystalline and amorphous phases. In the present work, we combined the possibilities of crystallization and anisotropic structures fabrication using femtosecond laser treatment at the 1250 nm wavelength of 200 nm thin amorphous GST225 films on silicon oxide/silicon substrates. A raster treatment mode and photoexcited surface plasmon polariton generation allowed us to produce mutually orthogonal periodic structures, such as scanline tracks (the period is 120 ± 10 µm) and laser-induced gratings (the period is 1100 ± 50 nm), respectively. Alternating crystalline and amorphous phases at the irradiated surfaces were revealed according to Raman spectroscopy and optical microscopy studies for both types of structures. Such periodic modulation leads to artificial optical and electrophysical anisotropy. Reflectance spectra in the near infrared range differ for various polarizations of probing light, and this mainly results from the presence of laser-induced periodic surface structures. On the other hand, the scanline tracks cause strong conductivity anisotropy for dc measurements in the temperature range of 200-400 K. The obtained results are promising for designing new GST225-based memory devices in which anisotropy may promote increasing the information recording density.

Kinetics of Silver Accumulation in Tissues of Laboratory Mice after Long-Term Oral Administration of Silver Nanoparticles.

Since ancient times, silver has been known for its pronounced bactericidal, antiviral and fungicidal properties. Currently, nanoparticles of this metal are widely used in the food, light and pharmaceutical industries, as well as in medicine. Silver in any form can have a toxic effect not only on pathogens, but also on healthy cells. The biological activity and bioavailability of silver preparations depend on the degree of their solubility in water. In addition, the maximum permissible concentration of soluble forms of silver is an order of magnitude lower than that of insoluble forms. This makes nanoparticles of silver with a hydrophilic coating that form stable colloidal solutions in aqueous media potentially unsafe objects. In this work, we studied the kinetics of the accumulation of silver nanoparticles with an average size of 34 ± 5 nm stabilized with polyvinylpyrrolidone in the organs of laboratory C57Bl/6 mice. The administration of nanoparticles was carried out orally for 30, 60, 120 and 180 days at the dose of 50 µg/day/animal. All the mice developed and gained weight normally during the experiment. No adverse effects were observed. Determination of the silver content in biological tissues of mammals was accomplished by neutron activation analysis. The masses and concentrations of silver in the brain and its different sections (hippocampus, cerebellum, cortex and remnants), as well as in the lungs, testes, liver, blood, kidneys, spleen and heart, were determined. The injection times at which the accumulation curves reached saturation were established. An extremely high accumulation of silver in the testes was shown at 120 days of administration, and a significant accumulation of silver in the lungs and brain was observed. The accumulation of silver in all parts of the brain except the cortex was significant, and its trend was similar to that in the whole brain.

Disturbance in Mammalian Cognition Caused by Accumulation of Silver in Brain.

The influence of daily prolonged administration of silver nanoparticles on the cognitive functions of a model mammal was studied. The accumulation of silver in the whole brain and the hippocampus, cerebellum, cortex and residual brain tissue of the mouse was investigated by highly precise and representative neutron activation analysis, and histological studies were conducted. Here, we show that long-term memory impairments were caused by the accumulation of silver nanoparticles in the brain and its subregions, such as the hippocampus, cerebellum and cortex, in a step-like manner by disturbance of hippocampal cell integrity. Three different approaches allowed us to observe this phenomenon and discover the reasons it occurred.

Fabricating Femtosecond Laser-Induced Periodic Surface Structures with Electrophysical Anisotropy on Amorphous Silicon.

One-dimensional periodic surface structures were formed by femtosecond laser irradiation of amorphous hydrogenated silicon (a-Si:H) films. The a-Si:H laser processing conditions influence on the periodic relief formation as well as correlation of irradiated surfaces structural properties with their electrophysical properties were investigated. The surface structures with the period of 0.88 and 1.12 µm were fabricated at the laser wavelength of 1.25 µm and laser pulse number of 30 and 750, respectively. The orientation of the surface structure is defined by the laser polarization and depends on the concentration of nonequilibrium carriers excited by the femtosecond laser pulses in the near-surface region of the film, which affects a mode of the excited surface electromagnetic wave which is responsible for the periodic relief formation. Femtosecond laser irradiation increases the a-Si:H films conductivity by 3 to 4 orders of magnitude, up to 1.2 × 10-5 S∙cm, due to formation of Si nanocrystalline phase with the volume fraction from 17 to 28%. Dark conductivity and photoconductivity anisotropy, observed in the irradiated a-Si:H films is explained by a depolarizing effect inside periodic microscale relief, nonuniform crystalline Si phase distribution, as well as different carrier mobility and lifetime in plane of the studied samples along and perpendicular to the laser-induced periodic surface structures orientation, that was confirmed by the measured photoconductivity and absorption coefficient spectra.

Nanoparticles Produced via Laser Ablation of Porous Silicon and Silicon Nanowires for Optical Bioimaging.

Modern trends in optical bioimaging require novel nanoproducts combining high image contrast with efficient treatment capabilities. Silicon nanoparticles are a wide class of nanoobjects with tunable optical properties, which has potential as contrasting agents for fluorescence imaging and optical coherence tomography. In this paper we report on developing a novel technique for fabricating silicon nanoparticles by means of picosecond laser ablation of porous silicon films and silicon nanowire arrays in water and ethanol. Structural and optical properties of these particles were studied using scanning electron and atomic force microscopy, Raman scattering, spectrophotometry, fluorescence, and optical coherence tomography measurements. The essential features of the fabricated silicon nanoparticles are sizes smaller than 100 nm and crystalline phase presence. Effective fluorescence and light scattering of the laser-ablated silicon nanoparticles in the visible and near infrared ranges opens new prospects of their employment as contrasting agents in biophotonics, which was confirmed by pilot experiments on optical imaging.

Effects of Prolonged Silver Nanoparticle Exposure on the Contextual Cognition and Behavior of Mammals.

Silver nanoparticles have been widely used in the lighting and food industries, in medicine, and in pharmaceutics as an antiseptic agent. Recent research demonstrates that, after prolonged oral administration, silver nanoparticles may cross the blood-brain barrier and accumulate in the brain in rather high amounts. In ex vivo experiments, it has also been shown that silver nanoparticles demonstrate neurotoxicity. The objective of this work was to answer the questions whether silver nanoparticles change cognitive and behavioral functions of mammals after prolonged administration if silver nanoparticles have accumulated in the brain. C57Bl/6 male mice were orally exposed to PVP-coated silver nanoparticles daily for 30, 60, 120 and 180 days. Control mice were exposed to distilled water. After that they were tested in the Open Field, Elevated Plus Maze, Light-Dark Box and contextual fear conditioning task. The data have shown that the experimental mice went through three periods of switching in the behavior caused by adaptation to the toxic silver nanoparticles: anxiety, appearance of research instinct and impairment of long-term memory. This provides evidence of the hazardous effect of silver nanoparticles, which appears after long periods of silver nanoparticle oral administration.

Paramagnetic properties of carbon-doped titanium dioxide.

This paper reports the experimental results on paramagnetic properties of carbon-doped titanium dioxide. The electron paramagnetic resonance study of the samples has been carried out both in dark and under illumination. The nature of defects and their dynamics under illumination of carbon-doped TiO_2 samples are discussed.

Effect of surface pressurization on the growth of α-Fe2O3 nanostructures.

By suitably pressurizing iron substrates under different conditions, the resulting α-Fe(2)O(3) nanostructures, formed by its direct thermal oxidation, can gradually change in succession from nanowires to nanoleaves and to micropillars as the pressure is increased. The inter-relation between the pressure conditions and the resulting nanostructure is studied by density functional calculations using ultrasoft pseudopotentials with a plane-wave basis method and with the generalized gradient approximation (GGA). It is shown that the shape of the formed nanostructures is primarily determined by the anisotropic activation energy and, as the latter is lowered, there is a shape change from wire to pillar. A simulation model of diffusion using the Monte Carlo method is applied in the 3-D (dimensional) case to show how the anisotropic activation energy influences the growth process of the α-Fe(2)O(3) nanostructure. The present study provides a way to control the shape of the nanostructures grown by the thermal-oxidation method.

Monte Carlo study for the growth of alpha-Fe2O3 nanowires synthesized by thermal oxidation of iron.

The growing mechanism of alpha-Fe(2)O(3) nanowires synthesized by thermal oxidation of iron is studied by the Monte Carlo method. Using a model of diffusion, the effects of synthesizing temperature, oxygen density and annealing on the morphology of the nanowires have been simulated. The results show that nanowires with a large head can only be obtained under the correct temperature and a sufficiently high density of oxygen. Under a low temperature or a low density of oxygen, particles can be obtained. And under a high temperature or after annealing, the nanowires will become thicker. The results are consistent with our experiments. This fact indicates that the growth of alpha-Fe(2)O(3) nanowires should be a diffusion process and provides an approach for improving the quality of the nanowires.

Effect of photonic crystal structure on the nonlinear optical anisotropy of birefringent porous silicon.

Anisotropic photonic crystal structures consisting of birefringent porous silicon layers with alternating porosity were fabricated. The in-plane birefringence formed as a result of anisotropic etching in Si(110) results in unique multilayered structures with two distinct photonic bandgaps for orthogonal light polarizations. Nonlinear optical studies based on the third-harmonic generation from these structures demonstrate variation in the symmetry of the nonlinear optical response.

Chemical modification of a porous silicon surface induced by nitrogen dioxide adsorption.

The effect of gaseous and liquid nitrogen dioxide on the composition and electronic properties of porous silicon (PS) is investigated by means of optical spectroscopy and electron paramagnetic resonance. It is detected that the interaction process is weak and strong forms of chemisorption on the PS surface, and the process may be regarded as an actual chemical reaction between PS and NO(2). It is found that NO(2) adsorption consists in forming different surface nitrogen-containing molecular groups and dangling bonds of Si atoms (P(b)-centers) as well as in oxidizing and hydrating the PS surface. Also observed are the formation of ionic complexes of P(b)-centers with NO(2) molecules and the generation of free charge carriers (holes) in the volume of silicon nanocrystals forming PS.