The crystal structure of a polymorph of copper phthalocyanine (CuPc) grown on a KCl substrate is redetermined by transmission electron diffraction. It has a triclinic unit cell containing one molecule; the crystal does not have a herringbone-type molecular arrangement, which is a common packing mode of planar phthalocyanines. The molecular packing is determined by the diffraction intensity with the aid of the calculation of molecular packing energy. One of the striking features of this polymorph is its stacking mode within a molecular column: the molecular stacking direction projected on a molecular plane is different by an angle of about 45 degrees from that of the alpha-modifications of platinum phthalocyanine (PtPc) and metal-free phthalocyanine (H(2)Pc). A powder X-ray diffraction profile calculated for the polymorph agrees well with that of so-called alpha-CuPc and Rietveld analysis for alpha-CuPc indicates that the CuPc crystals grown on KCl are actually alpha-CuPc; hence, alpha-CuPc is not isostructural with either alpha-PtPc or alpha-H(2)Pc. On the basis of the present results and the reported crystal structures of the planar phthalocyanines that form molecular columns, the polymorphs of the phthalocyanines can be classified into four types distinguished by the molecular stacking mode within the column: alpha(x)-, alpha(+)-, beta(x)- and beta(+)-types.

The crystal growth of isotactic polystyrene (it-PS) is investigated in very thin, 11 nm thick films. The it-PS crystals grown in the thin films show quite different morphology from that in the bulk. With decreasing crystallization temperature, the branching morphology in a diffusion field appears: dendrite and compact seaweed. The branching morphology is formed through a morphological instability caused by the gradient of film thickness around a crystal; the thicker the film thickness, the larger the lateral growth rate of crystals. Regardless of the morphological change, the growth rate as well as the lamellar thickness depends on crystallization temperature as predicted by the surface kinetics.

Epitaxial films of perylene-3,4,9,10-tetracarboxylic-dianhydride (PTCDA) on graphite (0001) were investigated by scanning tunneling microscopy. Molecular image contrast of PTCDA was found to depend strongly upon the molecular orientation and the position on graphite. In particular, the periodic discrepancy between PTCDA and graphite lattice points results in a modulation of contrast, which can be used to determine the epitaxial relation of PTCDA relative to the substrate accurately. By analyzing this modulation of contrast, we determined two kinds of epitaxial orientation of PTCDA. These orientations have no exact commensurate relation with graphite, but every lattice point of PTCDA lies on a lattice line parallel to the a axis (or b axis) of graphite. This specific feature contributes to decreasing the interfacial energy. The contrast mechanism of adsorbed molecules is also discussed.