Complex crystallization dynamics in amorphous germanium observed with dynamic transmission electron microscopy

Crystallization of amorphous germanium (a-Ge) by laser or electron beam heating is a remarkably complex process that involves several distinct modes of crystal growth and the development of intricate microstructural patterns on the nanosecond to ten microsecond time scales. Here we use dynamic transmission electron microscopy (DTEM) to study the fast, complex crystallization dynamics with 10 nm spatial and 15 ns temporal resolution. We have obtained time-resolved real-space images of nanosecond laser-induced crystallization in a-Ge with unprecedentedly high spatial resolution. Direct visualization of the crystallization front allows for time-resolved snapshots of the initiation and roughening of the dendrites on submicrosecond time scales. This growth is followed by a rapid transition to a ledgelike growth mechanism that produces a layered microstructure on a time scale of several microseconds. This study provides insights into the mechanisms governing this complex crystallization process and is a dramatic demonstration of the power of DTEM for studying time-dependent material processes far from equilibrium.

First principles study of magnetism in divalent Eu perovskites

A comparative first principles study has been carried out for EuLiH3 (ELH) and EuTiO3 (ETO) using the generalized gradient approximation +U approach. While ELH exhibits ferromagnetic ground state for all volumes, the magnetic ground state of ETO has the tendency to switch from G-type antiferromagnetic to a ferromagnetic state with change in volume. The marked difference in magnetic behavior and magnitude of the nearest neighbors exchange interaction of both the compounds are shown to be related to the difference in their respective electronic structure near the Fermi level. The Ti 3d states are shown to play predominant role in weakening the strength of the exchange interaction in ETO.

Chemical bond approach to determining conductivity band gaps in amorphous chalcogenides and pnictides

The minimum energy required for the formation of conjugate pair of charged defects is found to be approximately equal to the experimental activation energy for d.c. conductivity in a number of amorphous chalcoganides and pnictides. This observation implies that the defect pair formation energy represents an intrinsic gap for transport in amorphous chalcogenides.

Pressure sensitive flow and constraint factor in amorphous materials below glass transition

The constraint factor, C (given by the hardness-yield strength ratio H/Y in the fully lastic regime of indentation), in metallic glasses, is greater than three, a reflection of the sensitivity of their plastic flow to pressure. Furthermore, C increases with increasing temperature. In this work, we examine if this is true in amorphous polymers as well, through experiments on amorphous poly(methyl methacrylate) (PMMA). Uniaxial compression as well as spherical indentation tests were conducted in the 248-348 K range to construct H/Y versus indentation strain plots at each temperature and obtain the C-values. Results show that C increases with temperature in PMMA as well. Good correlation between the loss factors, measured using a dynamic mechanical analyzer, and C, suggest that the enhanced sensitivity to pressure is possibly due to beta-relaxation. We offer possible mechanistic reasons for the observed trends in amorphous materials in terms of relaxation processes.

Role of free volume in strain softening of as-cast and annealed bulk metallic glass

Plasticity in amorphous alloys is associated with strain softening, induced by the creation of additional free volume during deformation. In this paper, the role of free volume, which was a priori in the material, on work softening was investigated. For this, an as-cast Zr-based bulk metallic glass (BMG) was systematically annealed below its glass transition temperature, so as to reduce the free volume content. The bonded-interface indentation technique is used to generate extensively deformed and well defined plastic zones. Nanoindentation was utilized to estimate the hardness of the deformed as well as undeformed regions. The results show that the structural relaxation annealing enhances the hardness and that both the subsurface shear band number density and the plastic zone size decrease with annealing time. The serrations in the nanoindentation load-displacement curves become smoother with structural relaxation. Regardless of the annealing condition, the nanohardness of the deformed regions is similar to 12-15% lower, implying that the prior free volume only changes the yield stress (or hardness) but not the relative flow stress (or the extent of strain softening). Statistical distributions of the nanohardness obtained from deformed and undeformed regions have no overlap, suggesting that shear band number density has no influence on the plastic characteristics of the deformed region.

Origin of anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films

Anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films are established as being due to photochemical modification of the surfaces, by photoemission studies. Mass measurements indicate that the giant thickness reduction on irradiation is predominantly due to the loss of material as a result of photogenerated volatile high vapor pressure oxide fractions on the surface. This extrinsic contribution contradicts the models of the phenomenon proposed so far, which are based purely on intrinsic structural transformations.

Correlation between conductivity or diffusivity and activation energy in amorphous solids

There exist many investigations of ionic transport in a variety of glasses. These studies exhibit strong correlation between ionic conductivity and activation energy: Typically, it is found that higher conductivity is associated with lower activation energies and vice versa. Although there are explanations for this at a phenomenological level, there is no consistent physical picture to explain the correlation between conductivity and activation energy. We have carried out molecular dynamics simulation as a function of the size of the impurity atom or diffusant (both neutral and charged) in a host amorphous matrix. We find that there is a maximum in self-diffusivity as a function of the size of the impurity atom suggesting that there is an appropriate size for which the diffusivity is maximum. The activation energy is found to be the lowest for this size of the impurity. A similar maximum has been previously found in other condensed phases, such as confined fluids and dense liquids, and has its origin in the levitation effect. The implications of this result for understanding ionic conductivity in glasses are discussed. Our results suggest that there is a relation between microscopic structure of the amorphous solid, diffusivity or conductivity, and activation energy. The nature of this relationship is discussed in terms of the levitation parameter showing that diffusivity is maximum when the size of the neck or doorway radius is comparable with the size of the diffusant. Our computational results here are in excellent agreement with independent experimental results of Nascimento et al. [Braz. J. Phys. 35, 626 (2005)] that structural features of the glass are important in determining the ionic conductivity.

Observation of three-photon absorption and saturation of two-photon absorption in amorphous nanolayered Se/As2S3 thin film structures

We have studied the nonlinear optical properties of nanolayered Se/As2S3 film with a modulation period of 10 nm and a total thickness of 1.15 mu m at two [1064 nm (8 ns) and 800 nm (20 ps)] wavelengths using the standard Z-scan technique. Three-photon absorption was observed at off-resonant excitation and saturation of two-photon absorption at quasiresonant excitation. The observation of the saturation of two-photon absorption is because the pulse duration is shorter than the thermalization time of the photocreated carriers in their bands and three-photon absorption is due to high excitation irradiance. (c) 2007 American Institute of Physics.

Fine Structure of the Rayleigh Line in Amorphous Substances

As is well known, when monochromatic light scattered by a liquid is examined under high resolution it exhibits a fine structure: an undisplaced central line and two lines on either side with wavelengths slightly different from that of the incident light. The appearance of the displaced components was first predicted by Brillouin1. On the basis of his theory, the observed displacements of frequency are regarded as a Doppler effect arising from the reflexion of the light wave by the progressive sound waves of thermal origin in the scattering medium. The frequency shift of the so-called Brillouin components is given by the formula where nu and c are the velocities of sound and light in the medium and theta is the angle of scattering. That the effect contemplated by Brillouin does arise in liquids and crystals is now a well-established experimental fact.

A modified least squares algorithm to treat associations in liquid alloys

The associated model for binary systems has been modified to include volume effects and excess entropy arising from preferential interactions between the associate and the free atoms or between the free atoms. Equations for thermodynamic mixing functions have been derived. An optimization procedure using a modified conjugate gradient method has been used to evaluate the enthalpy and entropy interaction energies, the free energy of dissociation of the complex, its temperature dependance and the size of the associate. An expression for the concentration—concentration structure factor [Scc (0)] has been deduced from the modified associated solution model. The analysis has been applied to the thermodynamic mixing functions of liquid Ga-Te alloys at 1120 K, believed to contain Ga2Te3 associates. It is observed that the modified associated solution model incorporating volume effects and terms for the temperature dependance of interaction energies, describes the thermodynamic properties of Ga-Te system satisfactorily.

Volume effects and associations in liquid alloys

The regular associated solution model for binary systems has been modified by incorporating the size of the complex as an explicit variable. The thermodynamic properties of the liquid alloy and the interactions between theA ?B type of complex and the unassociated atoms in anA-B binary have been evaluated as a function of relative size of the complex using the activity coefficients at infinite dilution and activity data at one other composition in the binary. The computational procedure adopted for determining the concentration of clusters and interaction energies in the associated liquid is similar to that proposed by Lele and Rao. The analysis has been applied to the thermodynamic mixing functions of liquid Al-Ca alloys believed to contain Al2Ca associates. It is found that the size of the cluster significantly affects the interaction energies between the complex and the unassociated atoms, while the equilibrium constant and enthalpy change for the association reaction exhibit only minor variation, when the equations are fitted to experimental data. The interaction energy between unassociated free atoms remains virtually unaltered as the size of the complex is varied between extreme values. Accurate data on free energy, enthalpy, and volume of mixing at the same temperature on alloy systems with compound forming tendency would permit a rigorous test of the proposed model.

Magnetic, electric, and dielectric properties of FeCo alloy nanoparticles dispersed in amorphous matrix

Nanocrystalline Fe53Co47 alloy was synthesized by a single-step transmetallation chemical method at room temperature. The Fe53Co47 alloy nanoparticles of 77 and 47 wt% were dispersed in silica matrix by the sol-gel process using tetraethyl orthosilcate. Structural studies reveal that the as-prepared alloy powders are in bcc phase and silica is in an amorphous state. The phase-transition temperature and Mossbauer spectra analysis of the Fe-Co alloy establishes the homogeneous alloy formation. A saturation magnetization of 218 emu/g was obtained for pure FeCo alloy at room temperature. Scanning electron microscopic analysis demonstrates the hollow-sphere morphology for FeCo alloy particles. Magnetic nanocomposite consisting of 47 wt% FeCo-silica shows enhanced thermal stability over the native FeCo alloy. Electrical and dielectric properties of 47 wt% FeCo-silica nanocomposites were investigated as a function of frequency and temperature. It was found that the dielectric constants and dielectric loss were stable throughout the measured temperature (310-373 K). Our results indicate that FeCo-silica nanocomposite is a promising candidate for high-frequency applications. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Optical properties change in amorphous (As2S3)(0.87)Sb-0.13 thin films by photo and thermal induced process

Exposure with above band gap light and thermal annealing at a temperature near to glass transition temperature, of thermally evaporated amorphous (As2S3)(0.87)Sb-0.13 thin films of 1 mu m thickness, were found to be accompanied by structural effects, which in turn, lead to changes in the optical properties. The optical properties of thin films induced by illumination and annealing were studied by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photo darkening or photo bleaching was observed in the film depending upon the conditions of the light exposure or annealing. These changes of the optical properties are assigned to the change of homopolar bond densities. (C) 2010 Elsevier B.V. All rights reserved.

Transport properties, structure, and radiation induced defect studies in amorphous carbon films

Amorphous conducting carbon films are prepared by plasma assisted chemical vapour deposition and their d.c. conductivity (similar to 100 Scm(-1)) is studied from 300K down to 4.2K. The films were irradiated by high energy ion beam(I+13, 170 MeV) with a dose of 10(13) ions/cm(2). As a result a marked decrease in conductivity by two to three orders in magnitude was observed. The structural changes and the defects in the films caused by ion irradiation are studied using photoluminescence, persistent photoconductivity, and ESR spectroscopy.

Regular versus alternating (FeS4)(n) chains: Magnetism in KFeS2 and CsFeS2

We report crystal magnetic susceptibility results of two S = 1/2 one-dimensional Heisenberg antiferromagnets, KFeS2 and CsFeS2. Both compounds consist of (FeS4)(n) chains with an average Fe-Fe distance of 2.7 Angstrom. In KFeS2, all intrachain Fe-Fe distances are identical. Its magnetic susceptibility is typical of a regular antiferromagnetic chain with spin-spin exchange parameter J = -440.7 K. In CsFeS2, however, the Fe-Fe distances alternate between 2.61 and 2.82 Angstrom. This is reflected in its magnetic susceptibility, which could be fitted with J = -640 K, and the degree of alternation, alpha = 0.3. These compounds form a unique pair, and allow for a convenient experimental comparison of the magnetic properties of regular versus alternating Heisenberg chains.