Chain folding and the structure of nylon 6.6 spherulites

Following the assignment of the 1329 and 1224 cm^?1 infrared bands to chain-folded conformations in nylon 6.6 by Koenig et al. examination of the infrared spectra of positively birefringent and negatively birefringent spherulitic films has been made. The spectra indicate extensive regular folding in negative spherulites but fewer folds or less regular folding in the positive spherulite structure.

The assignment of the infrared fold bands to modes of vibration of the repeat unit is discussed with reference to the spectra of films with varying extents of N deuteration (normal 6.6, disordered regions deuterated, N deutero 6.6, disordered regions hydrogenated).

Electron micrographs of negative spherulites are analyzed with the infrared and previous evidence. We suggest they are built up of single-crystal lamellae of 0.2 to 0.3 μ lateral dimensions packed with a preferential orientation of the lamellae planes parallel to the radial direction but otherwise randomly oriented.     

F-Zentren und Kolloide in der amorphen,hexagonalen und kubischen Phase von LiJ

By simultaneous evaporation of LiI and Li onto a cooled substrate F centers can be produced in the hexagonal (78 K<T _K <200 K) and amorphous (T _K <78 K) phase of one and the same salt. In both modifications there exist two types of centers F and F^*. The F^* center differs from the cubic F center (T _d -symmetry) by a nearby Frenkel defect. In hexagonal films the normal F band peaks at 2.58 eV, whereas the transitions of the F^* center appear at 2.92 and 2.58 eV too. Polarized irradiation at 20 K causes a dichroic behaviour of the F^* centers. Both types of centers can be transformed into one another photochemically. In the amorphous phase all transitions are shifted to lower energies by about 0.1 eV. After the phase change amorphous→hexagonal the absorption bands shift back by the same amount of energy. AboveT _K =230 K the excess metal forms colloids. The absorption bands are due to colloidal centers embedded in the crystalline material (2.25 eV) and films adsorbed to the crystallites (3.1 eV), respectively. By annealing a particle growth can be observed. After electrolytic colouration cubic single crystals of LiI exhibit an absorption band peaking at 2.36 eV. However, it is not yet sure, if this band is allowed to be ascribed to F centers.     

The Great Myths of Polymer Melt Rheology,Part I: Comparison of Experiment and Current Theory

Abstract

Star polymers consisting of poly(?‐caprolactone), (PCL), grafted onto third generation dendrimer, which had hyperbranched and dendron cores, were studied by polarized light microscopy together with reference linear PCL. The degree of polymerization of the PCL arms in the star polymers ranged between 14 and 81. The star polymers exhibited a greater tendency than the linear polymers to form spherulites. It is suggested that the preference of the star polymers for forming spherulites is due to the presence of amorphous material—dendritic cores and PCL cilia—between crystal lamellae that generates the necessary pressure to force the lamellae to diverge at lamellar branch points. The linear growth rate data followed a single crystallization regime. The fold surface free energy was higher for the star polymers than for their linear analogs. It is proposed that the presence of the large and rigid dendritic cores on the fold surfaces of the star polymer crystals increases the fold surface energy.     

ZnSe films deposited on crystalline GaAs and amorphous quartz substrates by means of pulsed laser ablation technique

ZnSe films were deposited by pulsed laser ablation on a crystalline GaAs substrate and on an amorphous quartz substrate. The deposition process was performed with the same growth parameters. The films were investigated by means of X-ray diffraction, reflectance and photoluminescence spectroscopy. The X-ray diffraction spectra have demonstrated that the films grow in a highly oriented way but having different orientations, i.e. the films deposited on GaAs grow (100)-oriented and the films deposited on quartz grow (111)-oriented. Reflectance spectra as a function of the temperature have been analysed by means of the classical oscillator model, in order to obtain the temperature dependence of the band gap energy. This gives results comparable to those of ZnSe single crystals for ZnSe on GaAs, but it is red-shifted for ZnSe on quartz, because of lattice and thermal strains. The photoluminescence measurements at T = 10 K confirm the better quality of ZnSe deposited on GaAs and show that pulsed laser ablation is a promising technique to grow films having intrinsic luminescence even on an amorphous substrate. Received 29 May 2002 Published online 31 October 2002 RID="a" ID="a"e-mail: giuseppe.perna@ba.infn.it     

Structure and Surface Morphology of Cd<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se Epitaxial Films

Cd_1–xMn _x Se (х = 0.03) epitaxial films are produced by the molecular beam condensation method in a vacuum chamber with a residual pressure of 10^–4 Pa on mica and glass substrates. It is established that at room temperature and at a substrate temperature of T = 573 K films of polycrystalline structure grow on the mica substrates, but films of both polycrystalline and amorphous structure grow on the glass substrates. It is shown that the polycrystalline Cd_1–xMn _x Se (х = 0.03) films, unlike the bulk crystals, have a sphalerite-type structure with a lattice parameter of a = 6.05 Å. Increasing the substrate temperature to 673 K leads to epitaxial growth with the direction [111]. Dark aggregates, observed on the film surface, are removed using a source of compensating Se vapors during the growth process. The optimal conditions for the production of structurally perfect epitaxial films are defined.     

Scanning force microscopy of the crystalline/amorphous interface of ultradrawn poly(ethylene)

We report on high-resolution experiments by Scanning Force Microscopy (SFM) indicating the tight folding of neighbouring molecular chains in Poly(Ethylene) (PE) crystals. Ultradrawn PE films were prepared in the stacked lamellar morphology exhibiting crystalline lamellae and amorphous parts. The [001] direction of the lamellae is aligned parallel to the substrate surface resulting in {hk0} planes perpendicular to the symmetry axis of the probing tip. This preparation technique allows the direct observation of the molecular arrangement in polymeric crystals as well as an investigation of the crystalline/amorphous interface by SFM: at lower magnification, crystalline and amorphous parts of the film can be distinguished clearly. High-resolution imaging on the crystalline lamellae reveals a PE pitch height of 0.26±0.02 nm while the interchain spacing measures 0.50±0.02 nm consistent with (100) lattice planes aligned parallel to the substrate surface. Finally, the molecular folding at the edges of the lamellae has been studied. Evidence is found for the adjacent reentry of individual molecules at the edge of (100) surfaces.     

Characterization of vacuum evaporated In - Se thin films

The InSe films of different thicknesses (290–730 mm) were deposited onto glass substrates under a pressure of 3×10^?5 Torr by vacuum evaporation method. The composition (In=53.50%, Se=46.50%) of this film was confirmed using Auger Electron Spectroscopy (AES). Thicknesses of the deposited films have been measured using a Multiple Beam Interferometry. The amorphous nature of the film is confirmed with X-ray diffractogram. From the transmittance spectra in the range of 500 nm-1200 nm, it is observed that the film showed direct allowed transition. Effect of thickness on the optical parameters such as the fundamental band gap, absorption constant, refractive index of InSe thin films are reported. Under low electric field (～ 1.5×10⁵ Vcm^?1), the results of DC conductivity measurements revealed that the variable range hopping is the dominant conduction mechanism. The values of localized states density, localization radius and hopping energy of this film are estimated as 5.57×10²⁰ cm^?3eV^?1, 0.84 Å and 0.247 eV, respectively.     

Characterization and electrical behavior of new lithium chalcoborate thin films

Thin films obtained with glasses of the B₂S₃Li₂S and B₂S₃Li₂SLiI systems, using a vacuum evaporation technique have been investigated. In each system, amorphous thin films and starting glasses have the same composition and similar conductivities, about 10^?4 and 10^?3Ω^?1cm^?1 respectively at 25°C. The deposition rate was in both cases 140 Å s^?1. However, a thermal treatment at 90°C of the thin films containing lithium iodide enhances the conductivity by a factor of 10 and leads to lower activation energy (0.18 eV). This behavior has been identified as a Phipps effect and can be attributed to a quick ion diffusion along thin film - substrate interface. This interfacial region was found to show unique conduction properties including a very low Li⁺ migration enthalpy.     

Comment on “oscillatory indirect interaction between adsorbed atoms — Non-asymptotic behavior in tight-binding models at realistic parameters” by K.H. Lau and W. Kohn

A sensitive infrared reflectance accessory suitable for the study of surface films on medium size single crystals is described. Oxide films formed on the (100), (110) and (111) crystal faces of aluminum in air, at room temperature, display nearly identical behavior with films approximately 10 Å thick absorbing as a single band near 940 cm^?. After 10⁴ sec at 570 °C, in oxygen, films formed on these crystals begin to display differences in band characteristics and growth kinetics. Between 10⁴ and 4 × 10⁴ sec the rates of growth on the (110) and (111) crystal faces are much greater than on the (100) face. Beyond 4 × 10⁴ sec the growth rate on the (100) face increases while the (110) and (111) growth rates approach zero. Limiting thicknesses reached after 4 × 10⁵ sec approach 3.4 × 10², 2.1 × 10² and 2.2 × 10² Å for (100), (110) and (111) faces, respectively. Oxide compositional differences were reflected by the number and form of the infrared bands after 10⁴ sec of oxidation. After 5 × 10⁴ sec the (100) face oxide was composed of two and possibly three oxide species as evidenced by several bands. Differences in bandwidth and frequency were observed between the (110) and (111) oxide films. The significance of such differences is discussed.     

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO2 thin films by DC magnetron sputtering

Titanium dioxide (TiO₂) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO₂ films has been analyzed by X-ray photoelectron spectroscopy. The TiO₂ films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO₂ into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO₂/p-Si have been fabricated. The leakage current density of unbiased films was 1 × 10⁻⁶ A/cm² at a gate bias voltage of 1.5 V and it was decreased to 1.41 × 10⁻⁷ A/cm² with the increase of substrate bias voltage to −150 V owing to the increase in thickness of interfacial layer of SiO₂. Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at −150 V. The capacitance at 1 MHz for unbiased films was 2.42 × 10⁻¹⁰ F and it increased to 5.8 × 10⁻¹⁰ F in the films formed at substrate bias voltage of −150 V. Dielectric constant of TiO₂ films were calculated from capacitance–voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at −150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to −150 V.     

Study of the electrical properties of thin SmS films at high pressures

The pressure-induced shift of impurity levels under hydrostatic compression (?1.9 × 10^?2 meV/MPa) at T = 300 K has been derived from measurements of the behavior with temperature of the electrical resistance of thin polycrystalline SmS films on glass substrates at different pressures. The difference between the pressure-induced shifts of impurity levels in thin films and single crystals has been attributed to the effect of elastic properties of the substrate material. It has been shown that the semiconductor-metal phase transition in SmS films does not occur at pressures of up to 1000 MPa, because the impurity levels triggering the mechanism of phase transition at such pressures are not in the conduction band.     

Schichten aus amorphem Eisen

Thin films of iron are condensed onto a substrate at 20 ?K. After condensation and during annealing the electrical resistance is measured and Debye-Scherrer-diagramms are taken. The structure of the films depends on the evaporation rate and the vacuum conditions during condensation. In a good vacuum (10^?6 Torr) and for a high evaporation rate (100 å/sec) the films grow crystalline. Greater residual gas pressures and a slow evaporation rate (5 å/sec) lead to amorphous films. The amorphous structure is supposed to be induced by residual oxygen. A method is described to produce amorphous films of iron also in a high vacuum by condensing simultaneously small additions of Fe-oxide, Fe-selenide, Fe-sulfide, Si or Ge on a substrate at 20 ?K. During annealing the amorphous films change into the body-centered cubic structure of α-iron within a narrow range of temperature. Si is found to be the most effective substance to prevent crystallisation. Admixtures of Cu, Ag, Pb or SiO only lead to a state of high disorder, they do not prevent crystallisation of the Fe-films at any temperature of condensation.     

Crystallization of thin selenium films

The effect of the crystallization temperature and the substrate material on the morphology of the crystals produced by the heating of amorphous selenium films have been studied by electron microscopy and microscopic electron diffraction. The transition from ordinary crystallization to spherulite crystallization is found to be governed primarily by the crystallization temperature, and the spherulite crystallization is observed only at low temperatures. The substrate material affects only the ratio of the rates at which various crystal faces grow; it does not affect the transition from one type of crystallization to another. On all substrates, spherulites form as a result of the splitting of initial single-crystal nuclei; the crystallography of the splitting is the same.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, Vol. 12, No. 3, pp. 28–31, March, 1969.     

The characteristic investigation of spray coated W incorporated in oxide thin films

W incorporated tin oxide (TO) thin films were grown via spray pyrolysis with various tungsten contents. The films were observed to be polycrystalline tetragonal crystal nature with (301) and (211) preferential planes. From EDX analysis, it was seen the tungsten concentrations in the TO films were slightly higher than ones in the starting solutions. Polyhedron-like and small rod like grains were observed in the SEM images. 3 at % W doped tin oxide film has minimum sheet resistance (44.67 Ohm) and resistivity (3.685 × 10^?3 Ohm cm) values and maximum figure of merit (75.74 × 10^?5 Ohm^?1) value. The optical band gap (E_g) of pure film raised from 3.84 to 3.91 eV with 3 at % W contribution level.     

Magnetic circular and linear dichroism of iron garnets thin films

Low temperature absorption, MCD and MLD spectra are reported for pure and substituted Y₃Fe₅O₁₂ thin films in the 13000–33000 cm^?1 spectral range. The materials were obtained by liquid phase epitaxial growth on a Gd₃Ga₅O₁₂ substrate. Above 19000 cm^?1 we demonstrate that our transmission experiments on garnet films provide the same information as do reflexion measurements on bulk crystals. Below 19000 cm^?1 however, the former are much more reliable and accurate. All our data indicate that the films are of excellent optical quality. MCD and MLD spectra show a considerably increased resolution as compared to the absorption spectrum and help in sorting out most of its numerous overlapping components. Finally we prove unambiguously that Clogston's theoretical interpretation is qualitatively correct in the 13000–23000 cm^?1 region and even probably at higher wavenumbers.     

Low energy electron diffraction studies of the surfaces of molecular crystals (ice,ammonia, naphthalene,benzene)

Low Energy Electron Diffraction (LEED) has been used to study the surface structures of thin films of molecular crystals. The samples were grown epitaxially on metal single crystal substrates at low temperatures. Both Pt(111) and Ag(111) surfaces were used as substrates in order to identify the influence of the substrate on molecular film structure. Previous observations of ice (0001) and naphthalene (001) surfaces on films grown on Pt(111) substrates [Surface Sci. 55 (1976) 413], were confirmed using the Ag(111) substrate. The NH₃(111) and benzene (111) surfaces were also studied on films grown on either substrate. All observed molecular crystal surfaces showed no evidence of surface reconstruction. To minimize sample charging and electron beam induced damage, LEED experiments were performed on samples of thickness less than 10?10² nm, with low energy electron exposures less than 1 C cm^?2. The maximum thickness and exposure values were characteristic of the particular molecular crystal. The relationship between the structure of the initial adsorbed monolayer and the molecular crystal orientation is discussed.     

Solid-state 13C NMR and synchrotron SAXS/WAXS studies of uniaxially-oriented polyethylene

We report solid-state ¹³C NMR and synchrotron wide-and small-angle X-ray scattering experiments (WAXS, SAXS) on metallocene linear low density polyethylene films (e.g., Exceed™ 1018 mLLDPE; nominally 1 MI, 0.918 density ethylene-hexene metallocene copolymer) as a function of uniaxial draw ratio, λ. Combined, these experiments provide an unambiguous, quantitative molecular view of the orientation of both the crystalline and amorphous phases in the samples as a function of draw. Together with previously reported differential scanning calorimetry (DSC), gas transport measurements, transmission electron microscopy (TEM), optical birefringence, small angle X-ray scattering (SAXS) as well as other characterization techniques, this study of the state of orientation in both phases provides insight concerning the development of unusually high barrier properties of the most oriented samples (λ=10). In this work, static (non-spinning) solid-state NMR measurements indicate that in the drawn Exceed^TM films both the crystalline and amorphous regions are highly oriented. In particular, chemical shift data show the amorphous phase is comprised increasingly of so-called “taut tie chains” (or tie chains under any state of tautness) in the mLLDPE with increasing draw ratio – the resonance lines associated with the amorphous phase shift to where the crystalline peaks are observed. In the sample with highest total draw (λ=10), virtually all of the chains in the non-crystalline region have responded and aligned in the machine (draw) direction. Both monoclinic and orthorhombic crystalline peaks are observed in high-resolution, solid-state magic-angle spinning (MAS) NMR measurements of the oriented PE films. The orientation is comparable to that obtained for ultra-high molecular weight HDPE fibers described as “ultra-oriented” in the literature. Furthermore, the presence of a monoclinic peak in cold-drawn samples suggests that there is an appreciable internal stress associated with the LLDPE. The results are confirmed and independently quantified by Herman's Orientation Function values derived from the WAXS measurements. The degree of orientation approaches theoretically perfect alignment of chains along the draw direction. We deduce from this observation that a high fraction of the non-crystalline chains are either tie chains that directly connect adjacent lamellae or are interlocking loops from adjacent lamellae. In either case, the chains are load-bearing and are consistent with the idea of “taut tie chains”. We note that transmission electron micrographs recorded for the ultra-oriented Exceed showed the lamellae are often appreciably thinner and shorter than they are for cast or blown Exceed 1018. Combined with higher crystallinity, the thinner lamellae statistically favor more tie chains. Finally, the remarkably large decrease in permeability of the λ=10 film is primarily attributed to the high degree of orientation (and loss of entropy) of the amorphous phase.     

On the direct contact between overgrowth and substrate through amorphous carbon layers

The influence of intermediate amorphous carbon layers of different thicknesses on the epitaxy of Cu on Au (111) platelets was investigated. The experimental results prove that under experimental conditions for which the so called “long range” effect has been detected, direct contact between overgrowth and substrate through the intermediate layers is possible, provided its thickness is below a certain critical value. For carbon films prepared at room temperature on Au (111) substrates in a vacuum of 10^?6 Torr, this value lies between 50A?and 70A?.     

X-ray photoelectron spectroscopic study of nitrogen incorporated amorphous carbon films embedded with nanoparticles

The effect of substrate bias on X-ray photoelectron spectroscopy (XPS) study of nitrogen incorporated amorphous carbon (a-C:N) films embedded with nanoparticles deposited by filtered cathodic jet carbon arc technique is discussed. High resolution transmission electron microscope exhibited initially the amorphous structure but on closer examination the film was constituted of amorphous phase with the nanoparticle embedded in the amorphous matrix. X-ray diffraction study reveals dominantly an amorphous nature of the film. A straight forward method of deconvolution of XPS spectra has been used to evaluate the sp³ and sp² contents present in these a-C:N films. The carbon (C 1s) peaks have been deconvoluted into four different peaks and nitrogen (N 1s) peaks have been deconvoluted into three different peaks which attribute to different bonding state between C, N and O. The full width at half maxima (FWHM) of C 1s peak, sp³ content and sp³/sp² ratio of a-C:N films increase up to −150 V substrate bias and beyond −150 V substrate bias these parameters are found to decrease. Thus, the parameters evaluated are found to be dependent on the substrate bias which peaks at −150 V substrate bias.     

Partial crystallization of silicon by high intensity laser irradiation

Commercial single crystal silicon wafers and amorphous silicon films piled on single crystal silicon wafers were irradiated with a femtosecond pulsed laser and a nanosecond pulsed laser at irradiation intensities between 10¹⁷ W/cm² and 10⁹ W/cm². In the single crystal silicon substrate, the irradiated area was changed to polycrystalline silicon and the piled silicon around the irradiated area has spindly column structures constructed of polycrystalline and amorphous silicon. In particular, in the case of the higher irradiation intensity of 10¹⁶ W/cm², the irradiated area was oriented to the same crystal direction as the substrate. In the case of the lower irradiation intensity of 10⁸ W/cm², only amorphous silicon was observed around the irradiated area, even when the target was single crystal silicon. In contrast, only amorphous silicon particles were found to be piled on the amorphous silicon film, irrespective of the intensity and pulse duration.Three-dimensional thermal diffusion equation for the piled particles on the substrate was solved by using the finite difference methods. The results of our heat-flow simulation of the piled particles almost agree with the experimental results.