The Effect of Transfer Printing on Pentacene Thin-Film Crystal Structure

The thermal deposition and transfer Printing method had been used to produce pentacene thin-films on SiO2/Si and plastic substrates (PMMA and PVP), respectively. X-ray diffraction patterns of pentacene thin films showed reflections associated with highly ordered polycrystalline films and a coexistence of two polymorph phases classified by their d-spacing, d(001): 14.4 and 15.4 A.The dependence of the c-axis correlation length and the phase fraction on the film thickness and printing temperature were measured. A transition from the 15.4 A phase towards 14.4 A phase was also observed with increasing film thickness. An increase in the c-axis correlation length of approximately 12% ~16% was observed for Pn films transfer printed onto a PMMA coated PET substrate at 100~120 C as compared to as-grown Pn films on SiO2/Si substrates. The transfer printing method is shown to be an attractive for the fabrication of pentacene thin-film transistors on flexible substrates partly because of the resulting improvement in the quality of the pentacene film.Comment: 5 pages, 5 figure

Density-functional investigation of the rhombohedral to simple cubic phase transition of arsenic

We report on our investigation of the crystal structure of arsenic under compression, focusing primarily on the pressure-induced A7 to simple cubic (sc) phase transition. The two-atom rhombohedral unit cell is subjected to pressures ranging from 0 GPa to 200 GPa; for each given pressure, cell lengths and angles, as well as atomic positions, are allowed to vary until the fully relaxed structure is obtained. We find that the nearest and next-nearest neighbor distances give the clearest indication of the occurrence of a structural phase transition. Calculations are performed using the local density approximation (LDA) and the PBE and PW91 generalized gradient approximations (GGA-PBE and GGA-PW91) for the exchange-correlation functional. The A7 to sc transition is found to occur at 21+/-1 GPa in the LDA, at 28+/-1 GPa in the GGA-PBE and at 29+/-1 GPa in the GGA-PW91; no volume discontinuity is observed across the transition in any of the three cases. We use k-point grids as dense as 66X66X66 to enable us to present reliably converged results for the A7 to sc transition of arsenic.Comment: To be published in Physical Review B; material supplementary to this article is available at arXiv:0810.169

Calculated phonon spectra of paramagnetic iron at the alpha-gamma phase transition

We compute lattice dynamical properties of iron at the bcc-fcc phase transition using dynamical mean-field theory implemented with the frozen-phonon method. Electronic correlations are found to have a strong effect on the lattice stability of paramagnetic iron in the bcc phase. Our results for the structural phase stability and lattice dynamical properties of iron are in good agreement with experiment.Comment: 4 pages, 2 figure

Diluted Random Fields in Mixed Cyanide Crystals

A percolation argument and a dilute compressible random field Ising model are used to present a simple model for mixed cyanide crystals. The model reproduces quantitatively several features of the phase diagrams altough some crude approximations are made. In particular critical thresholds x_c at which ferroelastic first order transitions disappear, are calculated. Moreover, transitions are found to remain first order down to x_c for all mixtures except for bromine, for which the transition becomes continuous. All the results are in full agreement with experimental data.Comment: 8 pages, late

First-principles calculations for the adsorption of water molecules on the Cu(100) surface

First-principles density-functional theory and supercell models are employed to calculate the adsorption of water molecules on the Cu(100) surface. In agreement with the experimental observations, the calculations show that a H2O molecule prefers to bond at a one-fold on-top (T1) surface site with a tilted geometry. At low temperatures, rotational diffusion of the molecular axis of the water molecules around the surface normal is predicted to occur at much higher rates than lateral diffusion of the molecules. In addition, the calculated binding energy of an adsorbed water molecule on the surfaces is significantly smaller than the water sublimation energy, indicating a tendency for the formation of water clusters on the Cu(100) surface.Comment: 5 pages, 3 figures, submitted to Phys. Rev.

Total Chiral Symmetry Breaking during Crystallization: Who needs a "Mother Crystal"?

Processes that can produce states of broken chiral symmetry are of particular interest to physics, chemistry and biology. Chiral symmetry breaking during crystallization of sodium chlorate occurs via the production of secondary crystals of the same handedness from a single "mother crystal" that seeds the solution. Here we report that a large and "symmetric" population of D- and L-crystals moves into complete chiral purity disappearing one of the enantiomers. This result shows: (i) a new symmetry breaking process incompatible with the hypothesis of a single "mother crystal"; (ii) that complete symmetry breaking and chiral purity can be achieved from an initial system with both enantiomers. These findings demand a new explanation to the process of total symmetry breaking in crystallization without the intervention of a "mother crystal" and open the debate on this fascinating phenomenon. We present arguments to show that our experimental data can been explained with a new model of "complete chiral purity induced by nonlinear autocatalysis and recycling".Comment: 5 pages, 4 figures, Added reference

Temperature dependence of the electronic structure of semiconductors and insulators

The renormalization of electronic eigenenergies due to electron-phonon coupling is sizable in many materials with light atoms. This effect, often neglected in ab-initio calculations, can be computed using the perturbation-based Allen-Heine-Cardona theory in the adiabatic or non-adiabatic harmonic approximation. After a short description of the numerous recent progresses in this field, and a brief overview of the theory, we focus on the issue of phonon wavevector sampling convergence, until now poorly understood. Indeed, the renormalization is obtained numerically through a q-point sampling inside the BZ. For q-points close to G, we show that a divergence due to non-zero Born effective charge appears in the electron-phonon matrix elements, leading to a divergence of the integral over the BZ for band extrema. Although it should vanish for non-polar materials, unphysical residual Born effective charges are usually present in ab-initio calculations. Here, we propose a solution that improves the coupled q-point convergence dramatically. For polar materials, the problem is more severe: the divergence of the integral does not disappear in the adiabatic harmonic approximation, but only in the non-adiabatic harmonic approximation. In all cases, we study in detail the convergence behavior of the renormalization as the q-point sampling goes to infinity and the imaginary broadening parameter goes to zero. This allows extrapolation, thus enabling a systematic way to converge the renormalization for both polar and non-polar materials. Finally, the adiabatic and non-adiabatic theory, with corrections for the divergence problem, are applied to the study of five semiconductors and insulators: a-AlN, b-AlN, BN, diamond and silicon. For these five materials, we present the zero-point renormalization, temperature dependence, phonon-induced lifetime broadening and the renormalized electronic bandstructure.Comment: 27 pages and 26 figure

Phonon dispersion and electron-phonon coupling in MgB_2 and AlB_2

We present a first principles investigation of the lattice dynamics and electron-phonon coupling of the superconductor MgB_2 and the isostructural AlB_2 within the framework of density functional perturbation theory using a mixed-basis pseudopotential method. Complete phonon dispersion curves and Eliashberg functions \alpha^2F are calculated for both systems. We also report on Raman measurements, which support the theoretical findings. The calculated generalized density-of-states for MgB_2 is in excellent agreement with recent neutron-scattering experiments. The main differences in the calculated phonon spectra and \alpha^2F are related to high frequency in-plane boron vibrations. As compared to AlB_2, they are strongly softened in MgB_2 and exhibit an exceptionally strong coupling to electronic states at the Fermi energy. The total coupling constants are \lambda_{MgB_2}=0.73 and \lambda_{AlB_2}=0.43. Implications for the superconducting transition temperature are briefly discussed.Comment: 10 pages, 4 figures, to appear in Phys. Rev. Let

Mixed valency in cerium oxide crystallographic phases: Determination of valence of the different cerium sites by the bond valence method

We have applied the bond valence method to cerium oxides to determine the oxidation states of the Ce ion at the various site symmetries of the crystals. The crystals studied include cerium dioxide and the two sesquioxides along with some selected intermediate phases which are crystallographically well characterized. Our results indicate that cerium dioxide has a mixed-valence ground state with an f-electron population on the Ce site of 0.27 while both the A- and C-sesquioxides have a nearly pure f^1 configuration. The Ce sites in most of the intermediate oxides have non-integral valences. Furthermore, many of these valences are different from the values predicted from a naive consideration of the stoichiometric valence of the compound

Ab initio studies of phonon softening and high pressure phase transitions of alpha-quartz SiO2

Density functional perturbation theory calculations of alpha-quartz using extended norm conserving pseudopotentials have been used to study the elastic properties and phonon dispersion relations along various high symmetry directions as a function of bulk, uniaxial and non-hydrostatic pressure. The computed equation of state, elastic constants and phonon frequencies are found to be in good agreement with available experimental data. A zone boundary (1/3, 1/3, 0) K-point phonon mode becomes soft for pressures above P=32 GPa. Around the same pressure, studies of the Born stability criteria reveal that the structure is mechanically unstable. The phonon and elastic softening are related to the high pressure phase transitions and amorphization of quartz and these studies suggest that the mean transition pressure is lowered under non-hydrostatic conditions. Application of uniaxial pressure, results in a post-quartz crystalline monoclinic C2 structural transition in the vicinity of the K-point instability. This structure, intermediate between quartz and stishovite has two-thirds of the silicon atoms in octahedral coordination while the remaining silicon atoms remain tetrahedrally coordinated. This novel monoclinic C2 polymorph of silica, which is found to be metastable under ambient conditions, is possibly one of the several competing dense forms of silica containing octahedrally coordinated silicon. The possible role of high pressure ferroelastic phases in causing pressure induced amorphization in silica are discussed.Comment: 17 pages, 8 figs., 8 Table