Peter Puschnig

Theoretical study of PTCDA adsorbed on the coinage metal surfaces, Ag(111), Au(111) and Cu(111)

A thorough understanding of the adsorption of molecules on metallic surfaces is a crucial prerequisite for the development and improvement of functionalized materials. A prominent representative within the class of π-conjugated molecules is 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) which, adsorbed on the Ag(111), Au(111) or Cu(111) surfaces, shows characteristic trends for work-function modification, alignment of molecular levels with the substrate Fermi energy and binding distances. We carried out density functional theory (DFT) calculations to investigate to what extent these trends can be rationalized on a theoretical basis. We used different density functionals (DF) including a fully non-local van der Waals (vdW) DF capable of describing dispersion interactions. We show that, rather independent of the DF, the calculations yield level alignments and work-function modifications consistent with ultra-violet photoelectron spectroscopy when the monolayer is placed onto the surfaces at the experimental distances (as determined from x-ray standing wave experiments). The lowest unoccupied molecular orbital is occupied on the Ag and Cu surfaces, whereas it remains unoccupied on the Au surface. Simultaneously, the work function increases for Ag but decreases for Cu and Au. Adsorption distances and energies, on the other hand, depend very sensitively on the choice of the DF. While calculations in the local density approximation bind the monolayer consistently with the experimental trends, the generalized gradient approximation in several flavors fails to reproduce realistic distances and energies. Calculations employing the vdW-DF reveal that substantial bonding contributions arise from dispersive interactions. They yield reasonable binding energies but larger binding distances than the experiments.

Characterization of Step-Edge Barriers in Organic Thin-Film Growth

Detailed understanding of growth mechanisms in organic thin-film deposition is crucial for tailoring growth morphologies, which in turn determine the physical properties of the resulting films. For growth of the rodlike molecule para-sexiphenyl, the evolution of terraced mounds is observed by atomic force microscopy. Using methods established in inorganic epitaxy, we demonstrate the existence of an additional barrier (0.67 electron volt) for step-edge crossing—the Ehrlich-Schwoebel barrier. This result was confirmed by transition state theory, which revealed a bending of the molecule at the step edge. A gradual reduction of this barrier in the first layers led to an almost layer-by-layer growth during early deposition stage. The reported phenomena are a direct consequence of the complexity of the molecular building blocks versus atomic systems.

ElaStic: A tool for calculating second-order elastic constants from first principles

a b s t r a c t Elastic properties play a key role in materials science and technology. The elastic tensors at any order are defined by the Taylor expansion of the elastic energy or stress in terms of the applied strain. In this paper, we present ElaStic, a tool that is able to calculate the full second-order elastic stiffness tensor for any crystal structure from ab initio total-energy and/or stress calculations. This tool also provides the elastic compliances tensor and applies the Voigt and Reuss averaging procedure in order to obtain an evalua- tion of the bulk, shear, and Young moduli as well as the Poisson ratio of poly-crystalline samples. In a first step, the space-group is determined. Then, a set of deformation matrices is selected, and the corre- sponding structure files are produced. In a next step, total-energy or stress calculations for each deformed structure are performed by a chosen density-functional theory code. The computed energies/stresses are fitted as polynomial functions of the applied strain in order to get derivatives at zero strain. The knowl- edge of these derivatives allows for the determination of all independent components of the elastic tensor. In this context, the accuracy of the elastic constants critically depends on the polynomial fit. Therefore, we carefully study how the order of the polynomial fit and the deformation range influence the numer- ical derivatives, and we propose a new approach to obtain the most reliable results. We have applied ElaStic to representative materials for each crystal system, using total energies and stresses calculated with the full-potential all-electron codes exciting and WIEN2k as well as the pseudo-potential code

The role of polymorphism in organic thin films: oligoacenes investigated from first principles

We investigate the cohesive properties of oligoacenes within the framework of density functional theory including van der Waals interactions. In comparison, we evaluate the local density approximation as well as gradient corrections, but also a widely used semiempirical procedure accounting for the long-range dispersive forces, in terms of their performance for the energetics of such weakly bound systems. Besides the cohesive energies we discuss in detail the surface energies which, in turn, allow for obtaining the crystal shapes based on Wulffs construction for the oligomer series from naphthalene to pentacene. In particular, we focus on comparing two different pentacene polymorphs, i.e. the so-called bulk structure and the thin film phase, the latter being predominately found in thin film growth. We not only study the impact of molecular conformation on the details of these polyhedra, but also the influence of the number of considered index planes and the role of the underlying exchange correlation functional. Based on the relaxed crystal structures for the two polymorphic phases, we compute the electronic band structures as well as the optical spectra. To account for excitonic effects in the latter, we solve the Bethe–Salpeter equation for the electron–hole pairs, thereby considering the coupling between resonant and anti-resonant terms.

Epitaxial growth of π-stacked perfluoropentacene on graphene-coated quartz.

Chemical-vapor-deposited large-area graphene is employed as the coating of transparent substrates for the growth of the prototypical organic n-type semiconductor perfluoropentacene (PFP). The graphene coating is found to cause face-on growth of PFP in a yet unknown substrate-mediated polymorph, which is solved by combining grazing-incidence X-ray diffraction with theoretical structure modeling. In contrast to the otherwise common herringbone arrangement of PFP in single crystals and “standing” films, we report a π-stacked arrangement of coplanar molecules in “flat-lying” films, which exhibit an exceedingly low π-stacking distance of only 3.07 Å, giving rise to significant electronic band dispersion along the π-stacking direction, as evidenced by ultraviolet photoelectron spectroscopy. Our study underlines the high potential of graphene for use as a transparent electrode in (opto-)electronic applications, where optimized vertical transport through flat-lying conjugated organic molecules is desired.

Hybridization of Organic Molecular Orbitals with Substrate States at Interfaces: PTCDA on Silver

We demonstrate the application of orbital k-space tomography for the analysis of the bonding occurring at metal-organic interfaces. Using angle-resolved photoelectron spectroscopy, we probe the spatial structure of the highest occupied molecular orbital and the former lowest unoccupied molecular orbital (LUMO) of one monolayer 3, 4, 9, 10-perylene-tetracarboxylic-dianhydride (PTCDA) on Ag(110) and (111) surfaces and, in particular, the influence of the hybridization between the orbitals and the electronic states of the substrate. We are able to quantify and localize the substrate contribution to the LUMO and thus prove the metal-molecule hybrid character of this complex state.

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.

Unexpected interplay of bonding height and energy level alignment at heteromolecular hybrid interfaces

Although geometric and electronic properties of any physical or chemical system are always mutually coupled by the rules of quantum mechanics, counterintuitive coincidences between the two are sometimes observed. The coadsorption of the organic molecules 3,4,9,10-perylene tetracarboxylic dianhydride and copper-II-phthalocyanine on Ag(111) represents such a case, since geometric and electronic structures appear to be decoupled: one molecule moves away from the substrate while its electronic structure indicates a stronger chemical interaction, and vice versa for the other. Our comprehensive experimental and ab-initio theoretical study reveals that, mediated by the metal surface, both species mutually amplify their charge-donating and -accepting characters, respectively. This resolves the apparent paradox, and demonstrates with exceptional clarity how geometric and electronic bonding parameters are intertwined at metal-organic interfaces.

Substrate-mediated band-dispersion of adsorbate molecular states

Charge carrier mobilities in molecular condensates are usually small, as the coherent transport, which is highly effective in conventional semiconductors, is impeded by disorder and the small intermolecular coupling. A significant band dispersion can usually only be observed in exceptional cases such as for π-stacking of aromatic molecules in organic single crystals. Here based on angular resolved photoemission, we demonstrate on the example of planar π-conjugated molecules that the hybridization with a metal substrate can substantially increase the delocalization of the molecular states in selective directions along the surface. Supported by ab initio calculations we show how this mechanism couples the individual molecules within the organic layer resulting in an enhancement of the in-plane charge carrier mobility.

High pressure x-ray study on anthracene

The crystalline structure of anthracene (C14H10) under high pressure was studied performing angle dispersive x-ray diffraction experiments using synchrotron radiation in combination with Rietveld refinements and rigid body approximation. High hydrostatic pressure was applied up to 27.8 GPa using a diamond anvil cell. Full structural information (molecular orientations and lattice constants) is given up to a pressure of 20.3 GPa. At the highest pressure of 22.7 GPa the unit cell volume is decreased by 36.8%. Fourier transformation of the diffracted intensities reveals the electron density distribution within the unit cell. A pressure induced increase of the electron densities between adjacent molecules is observed. These findings are shown to be in agreement with theoretical calculations and hint towards the evolution of the anisotropic conductivity with pressure.