Branched crystal morphology of linear polyethylene crystallized in a two-dimensional diffusion-controlled growth field

The branched crystal morphology of linear polyethylene formed at various temperatures from thin films has been studied by atomic-force microscopy (AFM), transmission electron microscopy (TEM), electron diffraction (ED) pattern and polymer decoration technique. Two types of branched patterns, i.e. dendrite and seaweed patterns, have been visualized. The fractal dimension d _f = 1.65 of both dendrite and some of seaweed patterns was obtained by using the box-counting method, although most of the seaweed patterns are compact. Selected-area ED patterns indicate that the fold stems tilt about 34.5^° around the b-axis and polymer decoration patterns show that the chain folding direction and regularity in two (200) regions are quite different from each other. Because of chain tilting, branched crystals show three striking features: 1) the lamella-like branches show two (200) regions with different thickness; 2) the crystals usually bend towards the thin region; 3) the thick region grows faster by developing branches, thus branches usually occur outside the thick region. The branched patterns show a characteristic width w, which gives a linear relationship with the crystallization temperature on a semilogarithmic plot. Received 15 March 2002 and Received in final form 29 April 2002     

Growth instabilities of vapor deposited films: atomic size versus deflection effect

Two previously suggested, physically distinct mechanisms for a growth instability of vapor deposited films, the finite atomic size effect and the particle deflection effect due to interatomic attraction, are reconsidered, further analyzed, and compared. We substantiate why the instability caused by interatomic attraction must be considered as the truly underlying instability mechanism. We demonstrate that aspects of the structure zone model of Movchan and Demchishin can also be consistently explained using the growth instability induced by particle deflection instead of the instability arising from the atomic size effect. Most significantly we show that, for vapor deposited amorphous Zr₆₅Al_7.5Cu_27.5-films, the growth instability due to the atomic size effect cannot be present. Received 12 December 2001 Published online 6 June 2002     

Growth of entropy stabilized quasicrystals

A simplified version of the model by Elser and Joseph for the process of growth of an entropically stabilized, two-dimensional quasicrystal with no dynamics in the bulk, is proposed. The phason fluctuations are modeled by a scalar field on a periodic lattice. The choice of the master equation for the growth is restricted by the requirement that its detailed balance solution describes the equilibrium fluctuations of the field with a quadratic Hamiltonian. The model is parametrized by the chemical potential bias and the microscopic surface tension coefficient . The phase diagram of the system on the plane (, ) shows several distinct regimes of growth, separated by relatively narrow transition zones. Within the regions corresponding to these regimes, the phason fluctuations do not depend on and . Analytic expressions for the spectra of phason fluctuations are obtained and confirmed by numerical simulation. Received 30 June 2000     

Noise-assisted mound coarsening in epitaxial growth

Two types of mechanisms are proposed for mound coarsening during unstable epitaxial growth: stochastic, due to deposition noise, and deterministic, due to mass currents driven by surface energy differences. Both yield the relation H=(RWL)² between the typical mound height W, mound size L, and the film thickness H. An analysis of simulations and experimental data shows that the parameter R saturates to a value which discriminates sharply between stochastic () and deterministic () coarsening. We derive a scaling relation between the coarsening exponent 1/z and the mound-height exponent which, for a saturated mound slope, yields . Received: 11 November 1997 / Revised in final form: 28 November 1997 / Accepted: 28 November 1997     

Correlation between growth of high-index faces, relative growth rates and crystallographic structure of crystal

According to contemporary crystal growth theories, crystals are bound by low-index faces which are the most slowly growing. However, high-index faces are observed in crystal habits more and more often. In this paper the growth of high-index faces is analysed from a crystallographic perspective. It is shown that the crystallographic structure of a given crystal, expressed by the trigonometric function of appropriate interfacial angles, influences to great degree the crystallisation process and the morphology of crystals, in particular the behaviour of high-index faces. Additionally, it is concluded that at particular crystallographic structure of a crystal, a given high-index face may exist in the habit and develop its size, although it grows much faster than the neighbouring faces. Received 31 July 2001     

Ehrlich-Schwoebel barrier controlled slope selection in epitaxial growth

We examine the step dynamics in a 1+1-dimensional model of epitaxial growth based on the BCF-theory. The model takes analytically into account the diffusion of adatoms, an incorporation mechanism and an Ehrlich-Schwoebel barrier at step edges. We find that the formation of mounds with a stable slope is closely related to the presence of an incorporation mechanism. We confirm this finding using a solid-on-solid model in 2+1 dimensions. In the case of an infinite step edge barrier we are able to calculate the saturation profile analytically. Without incorporation but with inclusion of desorption and detachment we find a critical flux for instable growth but no slope selection. In particular, we show that the temperature dependence of the selected slope is solely determined by the Ehrlich-Schwoebel barrier which opens a new possibility in order to measure this fundamental barrier in experiments. Received 11 May 1999 and Received in final form 6 November 1999     

Crystallization kinetics and crystal morphology in thin poly(ethylene oxide) films

We present a detailed study of the kinetics of crystallization for thin films of poly(ethylene oxide) (PEO). Measurements of the growth rate have been carried out using optical-microscopy techniques on films of monodisperse PEO. Films with thicknesses from 13 nm to ~2 m were crystallized isothermally at temperatures ~20°C below the melting point. A remarkable non-monotonic slowing-down of the crystal growth is observed for films with thickness less than ~400 nm. The changes in the growth rate from bulk-like values is significant and corresponds to a factor of 40 decrease for the thinnest films studied. The morphologies of isothermally crystallized samples are studied using atomic-force microscopy. We find that a morphology, similar to diffusion-controlled growth (dendritic growth and densely branched growth), is observed for films with h < 150 nm. In addition, changes in the morphology occur for thicknesses consistent with changes in the growth rate as a function of film thickness.     

The origin of disorder in CH 3 HgX (X = Cl, Br and I) crystals investigated by temperature dependent Raman spectroscopy

Methyl-mercury(II) halides CH₃HgX (X = Cl, Br and I) were studied by means of temperature dependent Raman spectroscopy from 10 K to 410 K. In addition to the previously reported soft phonons, new changes in the low frequency spectra were observed at T ≈ 70 K in CH₃HgBr and at T ≈ 100 K in CH₃HgI. The bandwidths of the two internal modes in CH₃HgBr, the CH₃ symmetric stretching band and the C-Hg-Br bending band, rise towards a local maximum at T ≈ 50 K as the temperature is raised from 10 K to 300 K. On the other hand the bandwidths of the two corresponding modes in CH₃HgI crystals monotonously increase with temperature, obeying an Arrhenius law. Besides the three phonon modes present in the Raman spectra of CH₃HgCl at room temperature, the fourth phonon band that has been observed at temperatures below 245 K might correspond to the freezing of methyl librations. The huge bandwidth of the C-Hg-Br bending mode could suggest the presence of additional weak bonding of a mercury atom with bromine atoms from other molecules, thus inducing positional disorder. Received 19 November 1999 and Received in final form 10 November 2000     

Steps and facets at the surface of soft crystals

We consider the shape of crystals which are soft in the sense that their elastic modulus μ is small compared to their surface tension γ, more precisely μa < γ where a is the lattice spacing. We show that their surface steps penetrate inside the crystal as edge dislocations. As a consequence, these steps are broad with a small energy which we calculate. We also calculate the elastic interaction between steps a distance d apart, which is a 1/d ² repulsion. We finally calculate the roughening temperatures of successive facets in order to compare with the remarkable shapes of lyotropic crystals recently observed by Pieranski et al. [#!Pieranski!#,#!EPJ!#]. Good agreement is found. Received 25 June 2001     

Photoinduced IR absorption in WO 3 : determination of the polaron binding energy

Photoinduced IR absorption measurements are reported on WO₃. A photoinduced midinfrared small polaron peak centered at 4800 cm^-1 (0.59 eV) was observed. The data were analyzed in the framework of the photon-assisted small-polaron hopping theory and briefly compared to previously published infrared absorption measurements in WO₃ and photoinduced IR absorption measurements in high T _c cuprates. Received 20 April 2001 and Received in final form 13 July 2001     

Structural phase transition in the 2D spin dimer compound SrCu 2 ( BO 3 ) 2

A displacive, 2nd order structural phase transition at T _s = 395 K from space group I 2 m below T _s to I 4/m c m above T _s has been discovered in the two-dimensional spin dimer compound SrCu₂(BO₃)₂. The temperature evolution of the structure in both phases has been studied by X-ray diffraction and Raman scattering, supplemented by differential scanning calorimetry and SQUID magnetometry. The implications of this transition and of the observed phonon anomalies in Raman scattering for spin-phonon and interlayer coupling in this quantum spin system will be discussed. Received 24 July 2000 and Received in final form 2 November 2000     

Raman cross section of spin ladders

We demonstrate that a two-triplet resonance strongly renormalizes the Raman spectrum of two-leg spin-ladders and moreover suggest this to be the origin of the asymmetry of the magnetic Raman continuum observed in CaV₂O₅. Received 25 April 2001 and Received in final form 9 May 2001     

Magnetic, electronic, dielectric and optical properties of Pr(Ca:Sr)MnO 3

The charge-ordered perovskite Pr_0.65Ca_0.28Sr_0.07MnO₃ was investigated by means of magnetic susceptibility, specific heat, dielectric and optical spectroscopy and electron-spin resonance techniques. Under moderate magnetic fields, the charge order melts yielding colossal magnetoresistance effects with changes of the resistivity over eleven orders of magnitude. The optical conductivity is studied from audio frequencies far into the visible spectral regime. Below the phonon modes hopping conductivity is detected. Beyond the phonon modes the optical conductivity is explained by polaronic excitations out of a bound state. ESR techniques yield detailed informations on the (H,T ) phase diagram and reveal a broadening of the linewidth which can be modeled in terms of activated polaron hopping. Received 9 August 2000     

Phase transitions sequence in pyrochlore Cd2Nb2O7 studied by IR reflectivity

The infrared reflectivity of Cd₂Nb₂O₇ single crystal was studied in the temperature interval of 10-540 K, together with complementary dielectric measurements. A ferroelectric soft mode was revealed above the ferroelectric phase transition at T _c = 196 K coupled with a central-mode type dispersion in the near-millimetre range. This proves the mixed displacive and order-disorder nature of the transition. Below T _c many new modes were detected due to lowering of the symmetry, especially below the previously suggested incommensurate transition at 85 K. Discussion of the possible phase transitions based on symmetry considerations is presented with the conclusion that the ferroelectric transition is proper with the F_1u symmetry of the order parameter, whereas the intermediate ferroelastic transition is improper and triggered by the coupling with the ferroelectric order parameter. Received 17 July 2000     

Temperature dependence of infrared conductivity of manganites (x = 0, 0.05 and 0.2)

The temperature dependence of the reflectivity spectra of three manganites ceramics with compositions Pr_0.7Ca_0.3MnO₃, Pr_0.7Ca_0.25Sr_0.05MnO₃ and Pr_0.7Ca_0.1Sr_0.2MnO₃ has been investigated by infrared reflectivity spectroscopy in the wave number range 0.005-1.1 eV. The compound Pr_0.7Ca_0.25Sr_0.05MnO₃ which shows the largest conductivity jump at the ferromagnetic-paramagnetic phase transition has been studied in details. The optical conductivity of this compound is deduced from the best fit to reflectivity spectra of a “double-damping Drude” model, itself derived from the factorized form of the dielectric function. Excellent agreement with Kramers-Kronig transformation is reported. The model allows in particular to discriminate the contributions to the optical conductivity of trapped charges (polarons) and mobile charge carriers. Received 20 July 1999 and Received in final form 15 October 1999     

Carbon nanotube bundles and thin layers probed by micro-Raman spectroscopy

Raman spectra of single-wall carbon nanotubes (CNTs) either in the form of micrometer sized bundles or thin layers prepared by dilution and sonication of powders have been compared. We have been able to collect the Raman spectrum of nanotube bundles that are not in touch with the substrate, and therefore not affected by interactions with the substrate surface. This spectrum resulted to be similar to that of the precursor nanotube powders, whereas relevant changes in the Raman spectrum are detected when the diluted powders form very thin layers on either metallic or insulating surfaces, as probed by confocal microraman imaging on well defined areas of the CNTs layers. In the case of thin layers, the intensity of the Raman D band, detected between 1 320 and 1 340 cm^-1 and ascribed to disorder effects, is strongly enhanced. This enhancement occurs independently on the kind of substrate. Received 2 September 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: sangalet@dmf.bs.unicatt.it     

Submillimeter and infrared spectroscopy on La0.85Sr0.15MnO3

The optical conductivity of La_0.85Sr_0.15MnO₃ single crystals was studied by means of submillimeter and infrared spectroscopy for frequencies cm^-1 and temperatures 10 K < T <300 K. The submillimeter conductivity follows the temperature dependence of the dc-data. The phonon spectrum of La_0.85Sr_0.15MnO₃ changes considerably below K revealing a structural phase transition induced by charge or orbital order. At T =10 K a number of phonon modes can be identified in addition to the room-temperature spectrum. The optical conductivity () in the mid-infrared reveals the characteristics of small polaron absorption. Below the magnetic ordering temperature the polaron binding energy is highly reduced, but the onset of charge order interrupts the formation of free charge carriers with a Drude-like behavior. The frequency and temperature dependence of in this regime qualitatively resembles the small polaron predictions by Millis et al. (Phys. Rev. B 54, 5405 (1996)). Received 5 November 1999     

Elastic interaction between defects in thin and 2D films

Elastic interactions between defects is investigated at the surface of thin layers, a question on which we have given a brief account [P. Peyla et al. Phys. Rev. Lett. 82, 787 (1999)]. Two isotropic defects do not interact in an unlimited medium, regardless of the spatial dimension, a result which can be shown on the basis of the Gauss theorem in electrostatics. Within isotropic elasticity theory, defects interact only (i) if they are, for example, at a surface (or at least if they feel a boundary), or if their action on the material is anisotropic (e.g. they create a non central force distribution, though the material elasticity is isotropic). It is known that two identical isotropic defects on the surface of a semi-infinite material repel each other. The repulsion law behaves as 1/r ³(r = defects separation). We first revisit the Lau-Kohn theory and extend it to anisotropic defects. Anisotropy is found to lead to attraction. We show that in thin films defects may either attract or repel each other depending on the local geometric force distribution caused by the defect. It is shown that the force distribution (or more precisely the forces configuration symmetry) fixes the exponent in the power law 1/r ⁿ (e.g. for a four-fold symmetry n = 4). We discuss the implication of this behaviour in various situations. We treat the interactions in terms of the symmetries associated with the defect. We argue that if the defects are isotropic, then their effective interaction in an unlimited 2D (or a thin film) medium arises from the induced interaction, which behaves as 1/r ⁴ for any defect symmetry. We shall also comment on the contribution to the interaction which arises from flexion of thin films. Received 7 October 2002 Published online 4 June 2003 RID="a" ID="a"e-mail: chaouqi.misbah@ujf-grenoble.fr     

Conductivity of ultrathin Pb films during growth on Si(111) at low temperatures

The dipole modes of non-parabolic quantum dots are studied by means of their current and density patterns as well as with their local absorption distribution. The anticrossing of the so-called Bernstein modes originates from the coupling with electron-hole excitations of the two Landau bands which are occupied at the corresponding magnetic fields. Non-quadratic terms in the potential cause an energy separation between bulk and edge current modes in the anticrossing region. On a local scale the fragmented peaks absorb energy in complementary spatial regions which evolve with the magnetic field. Received 3 December 2001 / Received in final form 5 April 2002 Published online 9 July 2002     

Optical investigation of the quasi two-dimensional monophosphate tungsten bronzes K x P 4 W 8 O 32 (x = 0 - 1.57)

The potassium doped monophosphate tungsten bronzes K_xP₄W₈O₃₂ are two-dimensional metals which show a metal-to-metal transition at a critical temperature which depends on the doping level. The metal-to-metal transition is accompanied by the formation of a commensurate charge density wave with wave vector (π/b,0) which is independent of the doping level. Undoped P₄W₈O₃₂, on the other hand, has two metal-to-metal transitions which are connected to the formation of incommensurate charge density waves. We measured the infrared reflectivity of the series K_xP₄W₈O₃₂ (x = 0 - 1.57) in the spectral range from 100 to 10 000 cm^-1 for room temperature and well below the critical temperature. Polarization-dependent infrared spectra find a two-dimensional behavior in the normal and the charge density wave state and show signatures of hybridization between one- and two-dimensional conduction bands. In undoped P₄W₈O₃₂ the essentials of the charge density wave state can be understood from the nesting vectors of the calculated Fermi surface and two gaps are observed in the infrared spectra. The gap sizes are a factor of about 2.5 bigger than the predictions from mean-field theory in the weak-coupling limit which suggests medium- or strong electron-phonon coupling. For potassium doped K_xP₄W₈O₃₂ one gap is observed in the charge density wave state. The energetics of the charge density formation may be dominated by the energy required for the lattice modulation. Received 27 April 2001 and Received in final form 21 September 2001