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Understanding and manipulating crystallization processes has been an important challenge for solution-processed organic thin films, both for fundamental studies and for fabricating thin films with near-intrinsic charge transport properties. We report an in situ X-ray scattering study of the crystallization of 2-decyl-7-phenyl-[1]benzothieno[3,2- b ][1]benzothiophene (Ph-BTBT-C 10 ) during its deposition from solution. At temperatures modestly below the smectic-E/crystalline phase boundary, the crystallization goes through a transient liquid crystal state before reaching the final stable crystalline phase. Significant dynamics occur in the first few seconds of the transition, which are observed through fluctuations in the X-ray scattering intensity, and are correlated with the time interval that the transient thin film coexists with the evaporating solvent. The transition to the stable crystalline phase takes minutes or even hours under these conditions, which may be a result of the asymmetry of the molecule. Transient phases are of potential interest for applications, since they can act as a route to self-assembly of organic thin films. However, our observations show that the long-lived monolayer-stacked intermediate state does not act as a template for the bilayer-stacked crystalline phase. Rather, the grain structure is replaced through nucleation, where the nucleation free-energy barrier is related to a potential barrier that prevents molecules to flip their long axis by 180°. 

We present a previously discovered but undescribed late Early Cretaceous vertebrate fauna from the Holly Creek Formation of the Trinity Group in Arkansas. The site from the ancient Gulf Coast is dominated by semi-aquatic forms and preserves a diverse aquatic, semi-aquatic, and terrestrial fauna. Fishes include fresh- to brackish-water chondrichthyans and a variety of actinopterygians, including semionotids, an amiid, and a new pycnodontiform, Anomoeodus caddoi sp. nov. Semi-aquatic taxa include lissamphibians, the solemydid turtle Naomichelys , a trionychid turtle, and coelognathosuchian crocodyliforms. Among terrestrial forms are several members of Dinosauria and one or more squamates, one of which, Sciroseps pawhuskai gen. et sp. nov., is described herein. Among Dinosauria, both large and small theropods ( Acrocanthosaurus , Deinonychus , and Richardoestesia ) and titanosauriform sauropods are represented; herein we also report the first occurrence of a nodosaurid ankylosaur from the Trinity Group. The fauna of the Holly Creek Formation is similar to other, widely scattered late Early Cretaceous assemblages across North America and suggests the presence of a low-diversity, broadly distributed continental ecosystem of the Early Cretaceous following the Late Jurassic faunal turnover. This low-diversity ecosystem contrasts sharply with the highly diverse ecosystem which emerged by the Cenomanian. The contrast underpins the importance of vicariance as an evolutionary driver brought on by Sevier tectonics and climatic changes, such as rising sea level and formation of the Western Interior Seaway, impacting the early Late Cretaceous ecosystem. 

In ferroelectric thin films and superlattices, the polarization is intricately linked to crystal structure. Here we show that it can also play an important role in the growth process, influencing growth rates, relaxation mechanisms, electrical properties and domain structures. This is studied by focusing on the properties of BaTiO₃thin films grown on very thin layers of PbTiO₃using x-ray diffraction, piezoforce microscopy, electrical characterization and rapid in-situ x-ray diffraction reciprocal space maps during the growth using synchrotron radiation. Using a simple model we show that the changes in growth are driven by the energy cost for the top material to sustain the polarization imposed upon it by the underlying layer, and these effects may be expected to occur in other multilayer systems where polarization is present during growth. This motivates the concept of polarization engineering as a complementary approach to strain engineering.

 

The properties of artificially grown thin films are strongly affected by surface processes during growth. Coherent X-rays provide an approach to better understand such processes and fluctuations far from equilibrium. Here we report results for vacuum deposition of C₆₀on a graphene-coated surface investigated with X-ray Photon Correlation Spectroscopy in surface-sensitive conditions. Step-flow is observed through measurement of the step-edge velocity in the late stages of growth after crystalline mounds have formed. We show that the step-edge velocity is coupled to the terrace length, and that there is a variation in the velocity from larger step spacing at the center of crystalline mounds to closely-spaced, more slowly propagating steps at their edges. The results extend theories of surface growth, since the behavior is consistent with surface evolution driven by processes that include surface diffusion, the motion of step-edges, and attachment at step edges with significant step-edge barriers.