Morphological and Structural Investigation of Sexithiophene Growth on KCl (100)

The morphology and structure of sexithiophene deposited on KCl (100) substrates was investigated by scanning force microscopy and specular X-ray diffraction measurements. Two different needle-like structures with {010} and {4̅11} contact planes have been observed as well as islands of almost upright standing sexithiophene molecules with a {100} contact plane. Furthermore an azimuthal alignment of all three crystal orientations was observed by X-ray diffraction pole figure measurements, and the growth directions reflect the 4-fold rotational symmetry of the substrate surface. In addition the analysis of crystals with {4̅11} and {100} contact planes unveiled that they share a common crystallographic direction which is explained by ledge directed epitaxy

The Epitaxial Growth of Self-Assembled Ternaphthalene Fibers on Muscovite Mica

The morphology and structure of 2,2′:6′,2″-ternaphthalene (NNN) deposited on muscovite mica(001) substrates was investigated by scanning force microscopy (SFM) and specular X-ray diffraction measurements. Consistently, both methods reveal the coexistence of needle-like structures with a {111} contact plane and {001} orientated island-like crystallites, which are built up by almost upright standing NNN molecules. Both orientations are characterized by a well-defined azimuthal alignment relative to the substrate surface, which is analyzed by X-ray diffraction pole figure (XRD-PF) measurements. Based on XRD-PF and SFM analysis, the azimuthal alignment of {001} orientated crystallites is explained by ledge-directed epitaxy along the fibers’ sidewalls. These fibers are found to orient along two dominant directions, which is verified and explained by a doubling of the energetically preferred molecular adsorption site by mirror symmetry of the substrate surface. The experimental findings are confirmed by force-field simulations and are discussed based on a recently reported growth model

Interface Properties of Organic <i>para</i>-Hexaphenyl/α-Sexithiophene Heterostructures Deposited on Highly Oriented Pyrolytic Graphite

It was recently reported, that heterostructures of <i>para</i>-hexaphenyl (p-6P) and α-sexithiophene (6T) deposited on muscovite mica exhibit the intriguing possibility to prepare lasing nanofibers of tunable emission wavelength. For p-6P/6T heterostructures, two different types of 6T emission have been observed, namely, the well-known red emission of bulk 6T crystals and additionally a green emission connected to the interface between p-6P and 6T. In this study, the origin of the green fluorescence is investigated by photoelectron spectroscopy (PES). As a prerequisite, it is necessary to prepare structurally similar organic crystals on a conductive surface, which leads to the choice of highly oriented pyrolytic graphite (HOPG) as a substrate. The similarity between p-6P/6T heterostructures on muscovite mica and on HOPG is evidenced by X-ray diffraction (XRD), scanning force microscopy (SFM), and optical spectroscopy. PES measurements show that the interface between p-6P and 6T crystals is sharp on a molecular level without any sign of interface dipole formation or chemical interaction between the molecules. We therefore conclude that the different emission colors of the two 6T phases are caused by different types of molecular aggregation

Epitaxy of Rodlike Organic Molecules on Sheet SilicatesA Growth Model Based on Experiments and Simulations

During the last years, self-assembled organic nanostructures have been recognized as a proper fundament for several electrical and optical applications. In particular, phenylenes deposited on muscovite mica have turned out to be an outstanding material combination. They tend to align parallel to each other forming needlelike structures. In that way, they provide the key for macroscopic highly polarized emission, waveguiding, and lasing. The resulting anisotropy has been interpreted so far by an induced dipole originating from the muscovite mica substrate. Based on a combined experimental and theoretical approach, we present an alternative growth model being able to explain molecular adsorption on sheet silicates in terms of molecule−surface interactions only. By a comprehensive comparison between experiments and simulations, we demonstrate that geometrical changes in the substrate surface or molecule lead to different molecular adsorption geometries and needle directions which can be predicted by our growth model

Color Tuning of Nanofibers by Periodic Organic–Organic Hetero-Epitaxy

We report on the epitaxial growth of periodic para-hexaphenyl (<i>p</i>-6P)/α-sexi-thiophene (6T) multilayer heterostructures on top of <i>p</i>-6P nanotemplates. By the chosen approach, 6T molecules are forced to align parallel to the <i>p</i>-6P template molecules, which yields highly polarized photoluminescence (PL)-emission of both species. The PL spectra show that the fabricated multilayer structures provide optical emission from two different 6T phases, interfacial 6T molecules, and 3-dimensional crystallites. By a periodical deposition of 6T monolayers and <i>p</i>-6P spacers it is demonstrated that the strongly polarized spectral contribution of interfacial 6T can be precisely controlled and amplified. By analyzing the PL emission of both 6T phases as a function of <i>p</i>-6P spacer thickness (Δ<i>d</i>_{<i>p</i>–6P}) we have determined a critical value of Δ<i>d</i>_{<i>p</i>–6P}≈ 2.73 nm where interfacial 6T runs into saturation and the surplus of 6T starts to cluster in 3-dimensional crystallites. These results are further substantiated by UPS and XRD measurements. Moreover, it is demonstrated by morphological investigations, provided by scanning force microscopy and fluorescence microscopy, that periodical deposition of 6T and <i>p</i>-6P leads to a significant improvement of homogeneity in PL-emission and morphology of nanofibers. Photoluminescence excitation experiments in combination with time-resolved photoluminescence demonstrate that the spectral emission of the organic multilayer nanofibers is dominated by a resonant energy transfer from <i>p</i>-6P host- to 6T guest-molecules. The sensitization time of the 6T emission in the 6T/<i>p</i>-6P multilayer structures depends on the <i>p</i>-6P spacer thickness, and can be explained by well separated layers of host–guest molecules obtained by organic–organic heteroepitaxy. The spectral emission and consequently the fluorescent color of the nanofibers can be efficiently tuned from the blue <i>via</i> white to the yellow-green spectral range