Spontaneous growth of single crystals of various shapes in tin-fullerite films

Changes in the structure and elemental and phase compositions of tin-fullerite films after their storage in air are investigated by X-ray diffraction, scanning electronic microscopy, atomic force microscopy, X-ray spectroscopic microanalysis, and Auger electron spectroscopy. Formation of the new phase Sn_xC₆₀, whisker tin and Sn_xC₆₀ crystals, and petal and flowerlike fullerite crystals under the action of internal stress is established.     

On the Abnormal Conductivity of the Surface (001) of Alkali Halide Crystals

Crystallography Reports - Surfaces (001) of alkali halide crystals (KCl, NaCl), which were obtained by cleavage in air and ultrahigh vacuum, have been studied by Auger electron spectroscopy. It is...     

Heterogeneous versus bulk nucleation of lysozyme crystals

Heterogeneous (on‐glass) protein crystal nucleation was separated from the bulk one in systems of thin protein solution layers, confined between two glass plates of custom made quasi two‐dimensional all‐glass cells, as well as by applying forced protein solution flow. Two commercial samples of hen‐egg‐white lysozyme, Seikagaku and Sigma were used as model proteins. Applying the classical technique of separation in time of nucleation and growth stages with protein solution layers of thickness 0.05 cm we found that the on‐glass crystal nucleation prevailed highly with Seikagaku HEWL, while on the opposite, bulk nucleated crystals represented the main crystal fraction in Sigma solution. Also using 0.05 cm solution layers nucleation rates were measured separately for the on‐glass and bulk protein crystals. The process was investigated by varying solution layer thicknesses as well, from 0.05 down to 0.01, 0.0065 and 0.002 cm. Studying the influence of the forced protein solution flow on HEWL crystal nucleation the classical double‐pulse technique was modified by separating the nucleation and growth stages not only in time, but simultaneously also in place. In this case we found that the ratio of on‐glass formed crystal nuclei to bulk nuclei depended on the flow velocity, but in different manner with Seikagaku HEWL and Sigma HEWL. A plausible explanation of our experimental results is that the bulk crystal nucleation occurs on foreign surfaces as well, e.g. on rests of source biomaterial, which are always present in the protein solutions. Moreover, biomaterial seems to be more active nucleant than glass. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bulk crystallisation of (00l) oriented fresnoite Sr2TiSi2O8 in glass-ceramics of the Sr-Ti-Si-K-B-O system

This paper shows that glass-ceramics containing highly surface and bulk preferentially oriented fresnoite Sr₂TiSi₂O₈ crystals can be synthesised by a simple isothermal heat treatment of suitable glass compositions in the Sr-Ti-Si-K-B-O system. For all tested compositions, crystallisation starts from the free surfaces of the specimens and propagates to bulk with time. If most of these compositions lead to (00l) preferential orientation at the specimens' surfaces, bulk crystal texture is very composition dependent. The effects of variation in K₂O and B₂O₃ contents on the crystallisation have been studied. It is shown that low K₂O and high B₂O₃ contents are required to keep the (00l) orientation from the surface into the bulk. This result seems to be explained by the viscosities of the initial and residual glasses at the temperature of crystallisation: a low viscosity leads to a fine and homogeneous microstructure with small and strongly (00l) bulk oriented crystals.     

Neodymium ion environment in germanate crystals and glasses

Absorption and fluorescence spectra are presented for neodymium-doped alkali germanate and bismuth germanate glasses and crystals. Narrower spectral components and a shift in intensity distribution toward shorter wavelengths for the composite bands corresponding to the principal neodymium absorption and fluorescence transitions are observed as the radius of the glass modifier ion is increased (Li⁺Na⁺K⁺). These changes in component band width and intensity distribution become more pronounced as the concentration of large radius modifier ion is increased, and result in effectively narrower widths for the fluorescent bands involved in laser emission. Optical spectra for neodymium in a sodium germanate single crystal show broad bands characteristic of those of glasses. Electron microprobe scans reveal non-uniform distribution and clustering of neodymium in alkali germanate crystals. Narrow, temperature sensitive bands similar to those of neodymium in other crystals are found for single crystal and polycrystalline neodymium-doped bismuth germanate, while the glass exhibits broad bands. Substitutional replacement of Bi³⁺ with Nd³⁺ in the bismuth germanate crystal lattice is indicated from the optical spectra but the environment of neodymium in crystalline sodium germanate appears to have only short-range order. The difficulty encountered in introducing neodymium into substitutional positions in alkali germanate crystals may result from the charge difference between neodymium and the alkali cations as well as the oxygen: germanium ratio of these compounds, which favors glass network formation rather than crystallization.     

Polarity identification of GaN bulk single crystals (0001) surface by Auger electron spectroscopy

An attempt to identify the polarity of (0001) polar surface of GaN bulk single crystals grown by high nitrogen pressure solution method has been made using Auger electron spectroscopy (AES). AES concentration depth profiles of the top layer in (0001) direction starting from both (0001) faces of the sample have been measured. Distinct difference in the Ga concentration at the sample surface of both faces has been observed. The dependence of Ga eoncentration on depth is also different for both faces of the sample.     

The as-Grown SiC (0001) Surface as Observed by Reflection Electron Microscopy

Reflection electron microscopy (REM), capable of imaging surfaces in high resolution, reveals that the risers and treads in the terrace growth surfaces of vapor grown SiC(0001) bulk crystals are characterized on a microscopic scale by growth steps. At the risers microscopic growth occurs by the ‘step flow mode’. At the treads, growth occurs by island formation and by operation of growth spirals.     

Growth and characterization of nano‐crystalline hydroxyapatite at physiological conditions

Pure, stable stoichimetric nano crystalline hydroxyapatite material was crystallized by double diffusion technique at physiological conditions, temperature at 37°C and pH at 7.4. The sample was sintered at 400°C, 750°C and 1200°C with equal interval of time. They were characterized by X‐ray diffraction studies, Fourier Transformation Infra‐Red analysis, Thermogravimetric analysis, Scanning Electron Microscopic studies and Atomic Force Microscopic studies. The X‐ray analysis confirmed that the grown crystals are to be the pure form of hydroxyapatite. Infra‐red studies confirmed CO free hydroxyapatite. Thermogravimetric studies showed the thermal stability of the hydroxyapatite crystals even at 1200°C. The presence of pores in the sintered sample was traced by scanning electron microscopy. Atomic force microscopy revealed the presence of nano crystalline HAP of size 0.958 nanometer in the samples grown using this technique. At higher temperature the deagglomeration of bulk phases and agglomeration of nano phases leads to the nano crystalline HAP were observed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Atomic force microscopy modified for studying electric properties of thin films and crystals. Review

Probe force microscopy continues growing in popularity as a method for studying surfaces of solids and control over crystals and thin films that are grown on various scientific and industrial setups. New modifications of the method increase the possibilities for recording various characteristics of the objects studied. An important role here is played by “electrical” force microscopy, the various modifications and practical applications of which are considered below, as well as the results obtained by this method.     

Reactions at the liquid silicon/silica glass interface

Experiments have been carried out to determine the nature and origin of the spots growing on silica glass surfaces in contact with liquid silicon during CZ–Si crystal growth. Silica glass ampoules were filled with silicon and tempered between 5 min and 40 h at a temperature (1693 K) slightly above the melting point of silicon. Cross sections of the ampoules with solidified silicon have been examined by scanning electron microscopy and optical polarization microscopy. In addition cross sections from commercial silica glass crucibles used in the Czochralski process or dipped into the silicon melt were investigated with the same methods. At the silicon/silica glass interface different reaction zone morphologies were detected. A solution-precipitation mechanism is suggested for the fast lateral growth of the reaction zone, which is proposed to consist of small cristobalite crystals embedded in a silica glass matrix.     

Experimental observations of the thermal stability of high-k gate dielectric materials on silicon

High-k dielectric materials including zirconium oxide and hafnium oxide produced by atomic layer deposition have been evaluated for thermal stability. As-deposited samples have been compared with rapid thermal annealed samples over a range of source/drain dopant activation temperatures consistent with conventional complimentary metal oxide semiconductor polysilicon gate processes. Results of this initial investigation are presented utilizing analyses derived from X-ray diffraction (XRD), X-ray reflectometry (XRR), medium energy ion spectroscopy, high resolution transmission electron microscopy (HRTEM), tunneling atomic force microscopy, scanning electron microscopy, Auger electron spectroscopy and secondary ion mass spectroscopy. Changes in interface and surface roughness, percent crystallinity and phase identification for each material as a function of anneal temperature have been determined by XRD, XRR and HRTEM. Finally, high-k wet etch issues are presented relative to subsequent titanium silicide blanket film resistivity values.     

Chemical characteristics of float glass surfaces

The regions near the top and bottom surfaces of float glass are chemically different from the bulk glass composition. In addition to the presence of tin oxide at the bottom surface and to a lesser extent at the top surface, differences are found in SiO₂, Na₂O, CaO, SO₃ and Fe₂O₃. The concentrations of Na₂O, CaO and SO₃ are lower at the top surface than in the bulk glass, while SiO₂ is higher. In the case of tin at the bottom surface and iron at both top and bottom surfaces, the components exist in complex concentration gradients. In addition, there are variations in oxidation state for tin, iron and sulfur. Tin appears to exist in both stannous and stannic states near the bottom surface. So far it has been found that iron at the top surface and sulfur at the bottom are largely in reduced states. Some consequences of these effects have been observed in physical and chemical behavior of the surface.     

Chromium doping of silicate glasses by field-assisted solid-state ion exchange

Field-assisted solid-state ion exchange (FASSIE) is a suitable way to dope glasses with metallic ions. This approach is a promising technique for the production of glass waveguides containing either bivalent or trivalent ions, allowing the doping of glass surfaces with multivalent ions which could not diffuse into the glass matrix by means of the usual thermal ion-exchange process in molten salt baths. In this paper, results on the diffusion of chromium in silicate glasses are presented. A metallic chromium film deposited on the top of the glass substrates was used as the metal ions supplier. The doped layers were investigated by secondary ion mass and Rutherford backscattering spectrometries, as well as by micro-Raman spectroscopy. Chromium entered the glass matrices for some hundreds of nanometers, depending on the process temperature and the applied electric field. Strong compositional modification of the treated glasses was detected, related to alkali and alkali-earth elements distribution. For field-assisted solid-state diffusion, borosilicate glasses seem to be more stable matrices than the soda-lime silicate ones.     

Durability of an As2S3 chalcogenide glass: Optical properties and dissolution kinetics

The durability of a As₂S₃ chalcogenide glass composition was studied in de-ionized water at different temperatures (60-90 °C) for different periods of time, up to 120 days. The evolutions of the chemical composition and the pH of the solutions as well as the optical transmission of bulk samples, in the 2-10 μm region, were measured as a function of corrosion time. Atomic force microscopy and optical microscopy were used to investigate the roughness of corroded surfaces and the evolution of surface defects. The water corrosion of As₂S₃ glass was found to follow a congruent dissolution mechanism, a possible glass-water reaction mechanism was proposed. The optical transmission of the glass was found to be affected by the corrosion. The optical loss increased from 4 to 21% with corrosion time, this variation was attributed to the texturation of the surface by the reaction of corrosion. Moreover, the experimental results show that high temperature value enhances the corrosion reaction: an activation energy of 103 ± 2 kJ/mol was computed from experimental measurements.     

Crystal growth and morphology of hindered phenol AO-60

Crystal growth of a hindered phenol compound, tetrakis [methylene-3-(3-5-ditert-butyl-4-hydroxy phenyl) propionyloxy] methane (trade name AO-60), was successfully recorded by optical microscopy (OM) equipped with a hot stage. The morphology of AO-60 crystals, grown at 100 °C from amorphous state, appeared in the form of tetragonal-sloped step growth. Further study using scanning electron microscopy (SEM) and atomic force microscopy (AFM) experimentally demonstrated that AO-60 crystals had a hopper-like morphology, which had occurred rarely in the condition of organic compound crystals but predominantly rather to inorganic compound crystals in the reported literatures. The morphological features observed on the crystal surfaces suggested step growth and hopper growth mechanism. Besides, a raising around the edge of the AO-60 hopper crystal was also experimentally characterized for the first time.     

Effect of organic acid vapors on the alteration of soda silicate glass

Organic acids were previously shown to be involved in the alteration of historic soda silicate glasses in humid atmospheres under museum storage conditions. The present study investigates the role of these pollutants on the visual, compositional and structural modification of soda silicate glasses. Replica glasses aged in humid or humid/acidic atmospheres under accelerated conditions were examined and compared using light microscopy, electron microprobe and Raman spectroscopy. The characteristic modifications induced by each atmosphere are described. In the acid polluted atmosphere the leaching process created a layer that retained the transparency of the glass but with a chemical structure hydrated and more polymerized following the loss of alkali and the associated non-bridging oxygens, and the formation of new bridging bonds. In an unpolluted humid atmosphere, the dissolution process caused disruption of the silicate network at the glass surface and formation of an opaque gel layer. The hydrated silicate species and the cations in this gel layer subsequently polymerized to form a new amorphous material, hydrated and more depolymerized than the original glass. This investigation confirms that organic acid pollutants are responsible for the modifications observed on altered historic soda silicate glasses in the collections of the National Museums of Scotland.     

The surface layer formed on zinc-containing glass during aqueous attack

The glass-water interaction is reviewed via an outline of the processes of bulk dissolution, selective leaching and surface enhancement. Special attention is paid to the nature and effects of surface films. Glasses of three compositions, each containing about one-fifth by weight Zn, are subjected to aqueous attack. Solution analysis confirms the roles of Na, Si and Zn in leaching, dissolution and surface enhancement, respectively. Proton-induced X-ray emission corroborates Zn enhancement in the glass surface and X-ray photoelectron spectroscopy fixes the Zn build-up to the first few nanometres. Powder X-ray diffraction examination identifies the specific structures of hemimorphite and Zn orthosilicate while transmission electron microscopy finds such phases to be distributed in a largely amorphous matrix. Infrared spectra are consistent with the presence of a modified silicate structure and additionally indicate that water is loosely bound in the reacted surface layer. Attack of a non-Zn glass by a Zn-containing solution shows the ion in solution produces a Zn surface layer while attack of a Zn glass by a Zn complexing solution shows a Zn layer forms preferentially to complexation. Hence Zn, in either the solid or solution, induces a thin, protective, solvated and partially crystalline silicate zone on a glass under aqueous attack.     

Study of the surface heterogeneity of topographic and electric nature by atomic force microscopy by the example of triglycine sulfate

Triglycine sulfate crystals with an ideal (010) cleavage plane are used as model objects to reveal problems in interpreting atomic force microscopy (AFM) images of surfaces with nonuniform charge distribution. Specific microrelief features of two types are found: lenslike formations with different contrast and rounded protrusions/valleys of different size but fixed height. An analysis of their evolution with a change in temperature and under an electric field and mechanical impacts has made it possible to separate relief elements from the crystal domain structure. The interpretation proposed is confirmed by the multimode AFM data. The specific features of the images of dynamic domains and aged domains (which cannot undergo polarization reversal) are studied. The domain-wall width found in the AFM measurements depends on the technique used and the specificity of probe-surface interaction; it varies from 9 to 2000 nm. The most reliable data on the domain-wall width in triglycine sulfate crystals are provided by piezoelectric force microscopy, according to which the wall width does not exceed 30 nm.     

Possible differences between the surface and bulk structure of glasses

Changes in cation co-ordination at glass surfaces (indicating an increase of the oxygen-to-cation ratio within the topmost superficial layers) are evidenced by comparing data acquired by spectroscopic techniques of different excitation depth. Based on these experimental results, a theoretical model is developed that predicts structural discrepancies between surface and bulk structure. Such reconstructed surfaces are of great importance for all kind of surface-related crystallization phenomena.     

Growth and characterization of two-dimensional crystals for communication and energy applications

This review article covers the growth and characterization of two-dimensional (2D) crystals of transition metal chalcogenides, h-BN, graphene, etc. The chemical vapor transport method for bulk single crystal growth is discussed in detail. Top-down methods like mechanical and liquid exfoliation and bottom-up methods like chemical vapor deposition and molecular beam epitaxy for mono/few-layer growth are described. The optimal characterization techniques such as optical, atomic force, scanning electron, and Raman spectroscopy for identification of mono/few-layer(s) of the 2D crystals are discussed. In addition, a survey was done for the application of 2D crystals for both creation and deterministic transfer of single-photon sources and photovoltaic systems. Finally, the application of plasmonic nanoantenna was proposed for enhanced solar-to-electrical energy conversion and faster/brighter quantum communication devices.