Nitrogen-doped graphene: efficient growth, structure, and electronic properties.

A novel strategy for efficient growth of nitrogen-doped graphene (N-graphene) on a large scale from s-triazine molecules is presented. The growth process has been unveiled in situ using time-dependent photoemission. It has been established that a postannealing of N-graphene after gold intercalation causes a conversion of the N environment from pyridinic to graphitic, allowing to obtain more than 80% of all embedded nitrogen in graphitic form, which is essential for the electron doping in graphene. A band gap, a doping level of 300 meV, and a charge-carrier concentration of ∼8×10(12) electrons per cm2, induced by 0.4 atom % of graphitic nitrogen, have been detected by angle-resolved photoemission spectroscopy, which offers great promise for implementation of this system in next generation electronic devices.

Intra- and intermolecular band dispersion in an organic crystal.

The high crystallinity of many inorganic materials allows their band structures to be determined through angle-resolved photoemission spectroscopy (ARPES). Similar studies of conjugated organic molecules of interest in optoelectronics are often hampered by difficulties in growing well-ordered and well-oriented crystals or films. We have grown crystalline films of uniaxially oriented sexiphenyl molecules and obtained ARPES data. Supported by density-functional calculations, we show that, in the direction parallel to the principal molecular axis, a quasi-one-dimensional band structure of a system of well-defined finite size develops out of individual molecular orbitals. In contrast, perpendicular to the molecules, the band structure reflects the periodicity of the molecular crystal, and continuous bands with a large dispersion were observed.

Single crystalline nature of para-sexiphenyl crystallites grown on KCl(100).

This work focuses on studies of the single crystal nature of para-sexiphenyl structures grown on freshly cleaved KCl(100) surfaces. Two different kinds of morphologies, namely terrace like structures and needle like structures, are found by atomic force microscopy as well as by electron microscopy. Regardless of the morphology the individual crystallites show highly regular shapes. The crystalline alignment and the degree of order of the crystallites on the surface are determined by X-ray diffraction. Several epitaxial alignments of para-sexiphenyl on KCl(100) are observed and all of them are perfectly aligned on the surface. The rocking curve widths of the organic crystallites do not exceed 800" which is approximately only the four fold of the substrates' ones. The single crystalline nature of para-sexiphenyl crystallites is proven by transmission electron microscopy, diffraction patterns, dark field imaging and high resolution techniques. Single crystalline terraced mounds reach diameters of several microns and heights of 50 nm. Single crystal needles show heights and breadths of more than 100 nm and lengths of several microns.

Crystallographic and morphological characterization of thin pentacene films on polycrystalline copper surfaces.

The degree of crystallinity, the structure and orientation of crystallites, and the morphology of thin pentacene films grown by vapor deposition in an ultrahigh vacuum environment on polycrystalline copper substrates have been investigated by x-ray diffraction and tapping-mode scanning force microscopy (TM-SFM). Depending on the substrate temperature during deposition, very different results are obtained: While at 77 K a long-range order is missing, the films become crystalline at elevated temperatures. From a high-resolution x-ray-diffraction profile analysis, the volume-weighted size of the crystallites perpendicular to the film surface could be determined. This size of the crystallites increases strongly upon changing temperature between room temperature and 333 K, at which point the size of individual crystallites typically exceeds 100 nm. In this temperature region, three different polymorphs are identified. The vast majority of crystallites have a fiber texture with the (001) net planes parallel to the substrate. In this geometry, the molecules are oriented standing up on the substrate (end-on arrangement). This alignment is remarkably different from that on single-crystalline metal surfaces, indicating that the growth is not epitaxial. Additionally, TM-SFM images show needlelike structures which suggest the presence of at least one additional orientation of crystallites (flat-on or edge-on). These results indicate that properties of thin crystalline pentacene films prepared on technologically relevant polycrystalline metal substrates for fast electronic applications may be compromised by the simultaneous presence of different local molecular aggregation states at all temperatures.