Orientation-Dependent Work-Function Modification Using Substituted Pyrene-Based Acceptors.

The adsorption of molecular acceptors is a viable method for tuning the work function of metal electrodes. This, in turn, enables adjusting charge injection barriers between the electrode and organic semiconductors. Here, we demonstrate the potential of pyrene-tetraone (PyT) and its derivatives dibromopyrene-tetraone (Br-PyT) and dinitropyrene-tetraone (NO2-PyT) for modifying the electronic properties of Au(111) and Ag(111) surfaces. The systems are investigated by complementary theoretical and experimental approaches, including photoelectron spectroscopy, the X-ray standing wave technique, and density functional theory simulations. For some of the investigated interfaces the trends expected for Fermi-level pinning are observed, i.e., an increase of the metal work function along with increasing molecular electron affinity and the same work function for Au and Ag with monolayer acceptor coverage. Substantial deviations are, however, found for Br-PyT/Ag(111) and NO2-PyT/Ag(111), where in the latter case an adsorption-induced work function increase of as much as 1.6 eV is observed. This behavior is explained as arising from a face-on to edge-on reorientation of molecules in the monolayer. Our calculations show that for an edge-on orientation much larger work-function changes can be expected despite the prevalence of Fermi-level pinning. This is primarily ascribed to a change of the electron affinity of the adsorbate layer that results from a change of the molecular orientation. This work provides a comprehensive understanding of how changing the molecular electron affinity as well as the adsorbate structure impacts the electronic properties of electrodes.

Charged and metallic molecular monolayers through surface-induced aromatic stabilization.

Large π-conjugated molecules, when in contact with a metal surface, usually retain a finite electronic gap and, in this sense, stay semiconducting. In some cases, however, the metallic character of the underlying substrate is seen to extend onto the first molecular layer. Here, we develop a chemical rationale for this intriguing phenomenon. In many reported instances, we find that the conjugation length of the organic semiconductors increases significantly through the bonding of specific substituents to the metal surface and through the concomitant rehybridization of the entire backbone structure. The molecules at the interface are thus converted into different chemical species with a strongly reduced electronic gap. This mechanism of surface-induced aromatic stabilization helps molecules to overcome competing phenomena that tend to keep the metal Fermi level between their frontier orbitals. Our findings aid in the design of stable precursors for metallic molecular monolayers, and thus enable new routes for the chemical engineering of metal surfaces.

Orientational ordering of nonplanar phthalocyanines on Cu(111): strength and orientation of the electric dipole moment.

In order to investigate the orientational ordering of molecular dipoles and the associated electronic properties, we studied the adsorption of chlorogallium phthalocyanine molecules (GaClPc, Pc=C32N8H16(-2) on Cu(111) by using the x-ray standing wave technique, photoelectron spectroscopy, and quantum mechanical calculations. We find that for submonolayer coverages on Cu(111) the majority of GaClPc molecules adsorb in a Cl-down configuration by forming a covalent bond to the substrate. For bilayer coverages the x-ray standing wave data indicate a coexistence of the Cl-down and Cl-up configurations on the substrate. The structural details established for both cases and supplementary calculations of the adsorbate system allow us to analyze the observed change of the work function.

Site-specific geometric and electronic relaxations at organic-metal interfaces.

The correlation between the geometric and electronic structures of Zn-phthalocyanine (ZnPc) and F16ZnPc on Cu(111) were studied by x-ray standing wave and angle-resolved photoemission spectroscopy. We found evidence for a distortion of the planar molecules upon adsorption, with the central Zn atom in the molecule protruding towards the substrate. This modifies the energy levels of both the molecule and the substrate, which appear as interface states. The site-specific geometric and electronic relaxations are an important effect for organic-metal interface energetics.

Internal structure of nanoporous TiO2/polyion thin films prepared by layer-by-layer deposition.

The internal structure of porous TiO2 films prepared by electrostatic layer-by-layer deposition was investigated. The films were prepared by alternate dipping of solid substrates into dispersions of TiO2 nanoparticles and polycations, polyanions, or pure buffer solution, respectively. The surface charge of the amphoteric TiO2 particles was controlled by the pH of the aqueous dispersions. The morphology of the film surface was investigated by means of scanning electron microscopy. It was found that the surface roughness strongly depends on the polymeric material used for the deposition process but is independent of the ionic strength of the solution or the molecular weight of the polyions. The samples with rough surfaces feature strong light scattering. The porosity and internal structure of the TiO2/polyelectrolyte films were investigated by adsorption/desorption of dye molecules. A crude estimate yields an internal surface that is up to 160 times the plane surface of the substrate for a film thickness of 1 microm. The composition of the films was investigated by X-ray photoelectron spectroscopy (XPS). Detection of the XPS signal after each deposition step of the first three dipping cycles shows a significant increase of the relative surface coverage of Ti after the TiO2 deposition step and of PSS after the PSS deposition step. For later dipping cycles, such an increase was also detectable but less prominent.