Crystal alignment of caffeine deposited onto single crystal surfaces via hot-wall epitaxy.

Defined crystal growth is highly demanded for technological applications but also fundamental research. Within this work, the crystal growth of the asymmetric molecule caffeine was studied on single crystalline surfaces of muscovite mica, sodium chloride and potassium chloride. While elongated needle-like crystals grow on muscovite mica and sodium chloride, smaller individual "bird-like" structures were observed on potassium chloride. Depending on the surface type and temperature, the disk-shaped caffeine molecules prefer either an edge-on or flat-on orientation with respect to the surface, but in each case, a defined crystallographic relation between the surface and caffeine crystallites was determined by using the X-ray pole figure technique. On muscovite mica and sodium chloride, needle-like crystallites with edge-on oriented molecules aligned mainly with the unit cell c-axis (which coincides with the long needle axis) along the [1-10]mica, [100]mica, [110]mica and [110]NaCl, [1-10]NaCl directions, respectively. Crystals consisting of flat-on oriented molecules on KCl showed also defined alignments with respect to the substrate, but due to the altered molecule-substrate contact, the b-axis aligned along [110]KCl and [1-10]KCl. Growth at elevated temperatures enabled changes in the crystal growth whereby more defined structures formed on NaCl. On KCl, the bird-like structures remained very similar, while caffeine on the mica surface at elevated temperatures resulted in even additional texture forming with the caffeine molecules now also favoring a flat-on orientation with respect to the surface. The systematic variation of various system parameters demonstrates how sensitive the growth behavior of caffeine on this variety of substrates is.

Multiple scattering in grazing-incidence X-ray diffraction: impact on lattice-constant determination in thin films.

Dynamical scattering effects are observed in grazing-incidence X-ray diffraction experiments using an organic thin film of 2,2':6',2''-ternaphthalene grown on oxidized silicon as substrate. Here, a splitting of all Bragg peaks in the out-of-plane direction (z-direction) has been observed, the magnitude of which depends both on the incidence angle of the primary beam and the out-of-plane angle of the scattered beam. The incident angle was varied between 0.09° and 0.25° for synchrotron radiation of 10.5 keV. This study reveals comparable intensities of the split peaks with a maximum for incidence angles close to the critical angle of total external reflection of the substrate. This observation is rationalized by two different scattering pathways resulting in diffraction peaks at different positions at the detector. In order to minimize the splitting, the data suggest either using incident angles well below the critical angle of total reflection or angles well above, which sufficiently attenuates the contributions from the second scattering path. This study highlights that the refraction of X-rays in (organic) thin films has to be corrected accordingly to allow for the determination of peak positions with sufficient accuracy. Based thereon, a reliable determination of the lattice constants becomes feasible, which is required for crystallographic structure solutions from thin films.

Organic surface-grown nanowires for functional devices.

Discontinuous organic thin film growth on the surface of single crystals results in crystalline nanowires with extraordinary morphological and optoelectronic properties. By way of being generated at the interface of organic and inorganic materials, these nanowires combine the advantages of flexible organic films with the defectless character of inorganic crystalline substrates. The development of destruction-free transfer and direct growth methods allows one to integrate the organic nanowires into semiconductor, metallic electronic or photonic platforms. This article details the mechanisms that lead to the growth of these nanowires and exemplifies some of the linear as well as non-linear photonic properties, such as optical wave guiding, lasing and frequency conversion. The article also highlights future potential by showing that organic nanowires can be integrated into optoelectronic devices or hybrid photonic/plasmonic platforms as passive and active nanoplasmonic elements.

Interface properties of organic para-hexaphenyl/α-sexithiophene heterostructures deposited on highly oriented pyrolytic graphite.

It was recently reported, that heterostructures of para-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.

Indexing of grazing-incidence X-ray diffraction patterns: the case of fibre-textured thin films.

Crystal structure solutions from thin films are often performed by grazing-incidence X-ray diffraction (GIXD) experiments. In particular, on isotropic substrates the thin film crystallites grow in a fibre texture showing a well defined crystallographic plane oriented parallel to the substrate surface with random in-plane order of the microcrystallites forming the film. In the present work, analytical mathematical expressions are derived for indexing experimental diffraction patterns, a highly challenging task which hitherto mainly relied on trial-and-error approaches. The six lattice constants a, b, c, α, ß and γ of the crystallographic unit cell are thereby determined, as well as the rotation parameters due to the unknown preferred orientation of the crystals with respect to the substrate surface. The mathematical analysis exploits a combination of GIXD data and information acquired by the specular X-ray diffraction. The presence of a sole specular diffraction peak series reveals fibre-textured growth with a crystallographic plane parallel to the substrate, which allows establishment of the Miller indices u, v and w as the rotation parameters. Mathematical expressions are derived which reduce the system of unknown parameters from the three- to the two-dimensional space. Thus, in the first part of the indexing routine, the integers u and v as well as the Laue indices h and k of the experimentally observed diffraction peaks are assigned by systematically varying the integer variables, and by calculating the three lattice parameters a, b and γ. Because of the symmetry of the derived equations, determining the missing parameters then becomes feasible: (i) w of the surface parallel plane, (ii) the Laue indices l of the diffraction peak and (iii) analogously the lattice constants c, α and ß. In a subsequent step, the reduced unit-cell geometry can be identified. Finally, the methodology is demonstrated by application to an example, indexing the diffraction pattern of a thin film of the organic semiconductor pentacenequinone grown on the (0001) surface of highly oriented pyrolytic graphite. The preferred orientation of the crystallites, the lattice constants of the triclinic unit cell and finally, by molecular modelling, the full crystal structure solution of the as-yet-unknown polymorph of pentacenequinone are determined.

Surface-Induced Phase of Tyrian Purple (6,6'-Dibromoindigo): Thin Film Formation and Stability.

The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6'-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π-π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds.

Grain Size and Interface Dependence of Bias Stress Stability of n-Type Organic Field Effect Transistors.

The effect of grain size and interface dependence of bias stress stability of C60-based n-type organic field effect transistors (OFETs) has been studied. It has been realized that, with increasing grain size of C60, the bias stress induced threshold voltage shift can be controlled and this effect is mainly attributed to the mechanism of charge trapping at grain boundaries. It is further studied that the growth of C60 on the surface of parylene at elevated substrate temperature leads to the creation of radicals at the interface between the active layer and the gate dielectric. These radicals help to improve the bias stress stability of C60-based n-type OFETs. For achieving the bias stress stability, we have presented a procedure of creation of radicals at the interface between C60 and parylene in single gate OFETs instead of dual gate OFETs.

Complex Behavior of Caffeine Crystallites on Muscovite Mica Surfaces.

Defined fabrication of organic thin films is highly desired in technological, as well as pharmaceutical, applications since morphology and crystal structure are directly linked to physical, electrical, and optical properties. Within this work, the directed growth of caffeine deposited by hot wall epitaxy (HWE) on muscovite mica is studied. Optical and atomic force microscopy measurements reveal the presence of caffeine needles exhibiting a preferable alignment in the azimuthal directions with respect to the orientation of the defined mica surface. Specular X-ray diffraction and X-ray diffraction pole figure measurements give evidence that the ß-polymorphic form of caffeine forms on the mica surface. All results consent that caffeine molecules have an edge-on conformation i.e. minimizing their interaction area with the surface. Furthermore, the azimuthal alignment of the long caffeine needle axis takes place along the [11̅0], [100], and [110] real space directions of mica; needles are observed every 60° azimuthally. While mica has a complex surface structure with mirror planes and lowered oxygen rows, the slightly disturbed 3-fold symmetry dictates the crystal alignment. This is different to previous findings for solution cast caffeine growth on mica. For HWE the needles align solely along the mica main directions whereby solution cast needles show an additional needle splitting due to a different alignment of caffeine with respect to the surface.

Efficient Exciton Diffusion and Resonance-Energy Transfer in Multilayered Organic Epitaxial Nanofibers.

Multilayered epitaxial nanofibers are exemplary model systems for the study of exciton dynamics and lasing in organic materials because of their well-defined morphology, high luminescence efficiencies, and color tunability. We use temperature-dependent continuous wave and picosecond photoluminescence (PL) spectroscopy to quantify exciton diffusion and resonance-energy transfer (RET) processes in multilayered nanofibers consisting of alternating layers of para-hexaphenyl (p6P) and α-sexithiophene (6T) serving as exciton donor and acceptor material, respectively. The high probability for RET processes is confirmed by quantum chemical calculations. The activation energy for exciton diffusion in p6P is determined to be as low as 19 meV, proving p6P epitaxial layers also as a very suitable donor material system. The small activation energy for exciton diffusion of the p6P donor material, the inferred high p6P-to-6T resonance-energy-transfer efficiency, and the observed weak PL temperature dependence of the 6T acceptor material together result in an exceptionally high optical emission performance of this all-organic material system, thus making it well suited, for example, for organic light-emitting devices.

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.

Geometrical structure and interface dependence of bias stress induced threshold voltage shift in C60-based OFETs.

The influence of the nature of interface between organic semiconductor and gate dielectric on bias stress electrical stability of n-type C60-based organic field effect transistors (OFETs) was studied. The bias stress induced threshold voltage (Vth) shift was found to depend critically on the OFET device structure: the direction of V(th) shift in top-gate OFETs was opposite to that in bottom-gate OFETs, while the use of the dual-gate OFET structure resulted in just very small variations in V(th). The opposite direction of Vth shift is attributed to the different nature of interfaces between C60 semiconductor and Parylene dielectric in these devices. The V(th) shift to more positive voltages upon bias stress in bottom-gate C60-OFET was similar to that observed for other n-type semiconductors and rationalized by electron trapping in the dielectric or at the gate dielectric/C60 interface. The opposite direction of Vth shift in top-gate C60-OFETs is attributed to free radical species created in the course of Parylene deposition on the surface of C60 during device fabrication, which produce plenty of hole traps. It was also realized that the dual-gate OFETs gives stable characteristics, which are immune to bias stress effects.

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.

Photo-Fries-based photosensitive polymeric interlayers for patterned organic devices.

This work reports on the investigation of the photosensitive polymer poly(diphenyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate) (PPNB), which undergoes the photo-Fries rearrangement upon illumination with UV-light, used as interfacial layers in organic electronic devices. Two cases were investigated: the use of a blend of PPNB with poly-vinylcarbazole (PVK) as an interlayer in para-sexiphenyl (PSP) based organic light emitting diodes (OLEDs) and the use of PPNB as gate dielectric layer in organic field effect transistors (OFETs). The photo-Fries rearrangement reaction causes a change of the polymer chemical structure resulting in a change of its physical and chemical properties. The electroluminescence spectra and emission of the PSP OLEDs are not affected when fabricated with a non-UV-illuminated PPNB:PVK blend. However, the electroluminescence is totally quenched in those OLEDs fabricated with UV-illuminated PPNB:PVK blend. Although the dielectric constant of PPNB increases upon UV-treatment, it is demonstrated that those OFETs built with UV-treated PPNB as gate dielectric have lower performance than those OFETs built with non-UV-treated PPNB. Furthermore, the effect of the UV-illumination of PPNB and PPNB:PVK blend on the growth of the small molecules C60 and PSP has been studied by atomic force microscopy. Using photolithography, this kind of photochemistry can be performed to spatially control and tune the optical and electrical performance of organic electronic devices.

Color tuning of nanofibers by periodic organic-organic hetero-epitaxy.

We report on the epitaxial growth of periodic para-hexaphenyl (p-6P)/α-sexi-thiophene (6T) multilayer heterostructures on top of p-6P nanotemplates. By the chosen approach, 6T molecules are forced to align parallel to the p-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 p-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 p-6P spacer thickness (Δd(p-6P)) we have determined a critical value of Δd(p-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 p-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 p-6P host- to 6T guest-molecules. The sensitization time of the 6T emission in the 6T/p-6P multilayer structures depends on the p-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 via white to the yellow-green spectral range.

Organic-organic heteroepitaxy of red-, green-, and blue-emitting nanofibers.

Self-assembly processes and organic-organic heteroepitaxy are powerful techniques to obtain highly ordered molecular aggregates. Here we demonstrate that combining both methods allows not only to fabricate highly crystalline and uniaxially oriented self-assembled nanofibers but also to tune their polarized emission. We show that submonolayer coverage of sexithiophene on top of para-sexiphenyl nanofibers is sufficient to change their emission color from blue to green. Triband emission in the red, green, and blue is generated in nanofibers with thicker sexithiophene coverage, where layers of co-oriented crystals are separated by green-emitting molecular sheets.