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.

Reversibility of temperature driven discrete layer-by-layer formation of dioctyl-benzothieno-benzothiophene films.

Film forming properties of semiconducting organic molecules comprising alkyl-chains combined with an aromatic unit have a decisive impact on possible applications in organic electronics. In particular, knowledge on the film formation process in terms of wetting or dewetting, and the precise control of these processes, is of high importance. In the present work, the subtle effect of temperature on the morphology and structure of dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) films deposited on silica surfaces by spin coating is investigated in situ via X-ray diffraction techniques and atomic force microscopy. Depending on temperature, bulk C8-BTBT exhibits a crystalline, a smectic A and an isotropic phase. Heating of thin C8-BTBT layers at temperatures below the smectic phase transition temperature leads to a strong dewetting of the films. Upon approaching the smectic phase transition, the molecules start to rewet the surface in the form of discrete monolayers with a defined number of monolayers being present at a given temperature. The wetting process and layer formation is well defined and thermally stable at a given temperature. On cooling the reverse effect is observed and dewetting occurs. This demonstrates the full reversibility of the film formation behavior and reveals that the layering process is defined by an equilibrium thermodynamic state, rather than by kinetic effects.

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.

Heart rate variability - a potential early marker of sub-acute post-stroke infections.

OBJECTIVE: Infection is the most relevant complication after acute ischemic stroke. Activity of the autonomic nervous system seems to control post-stroke immunodepression. We investigated heart rate variability (HRV) indices that reflect autonomic readjustments as predictors of post-stroke infection. MATERIALS AND METHODS: Forty-three patients with acute ischemic stroke were enrolled in a prospective study. The predictability of sub-acute infections (day 4 ± 1 after admission) was investigated in 34 patients without acute infection by means of HRV indices obtained in the acute period (48 h after admission). RESULTS: Sub-acute infection could be predicted in patients without clinical or paraclinical (white blood cell count and C-reactive protein) signs of infection in the acute period at (i) day: increased HFnorm, reduced LFnorm and LF/HF; (ii) night: reduced LF and VLF (P < 0.05). CONCLUSIONS: HRV indices are candidates for early markers of developing post-stroke infections, preceding routine blood samples. Thus, HRV-based early diagnosis of post-stroke infection should be investigated in more detail as it may have implications as a novel tool for timely and appropriate treatment. A corresponding continuous HRV-based risk assessment using the ECG provided by the routine stroke monitoring system would be possible without any additional burden for patients and staff.

Evidence for temperature-dependent electron band dispersion in pentacene.

Evidence for temperature-dependent electron band dispersion in a pentacene thin film polymorph on graphite is provided by angle- and energy-dependent ultraviolet photoelectron spectroscopy. The bands derived from the highest occupied molecular orbital exhibit dispersion of approximately 190 meV at room temperature, and approximately 240 meV at 120 K. Intermolecular electronic coupling in pentacene thin films is thus confirmed to be dependent on temperature and possibly crystal structure, as suggested by additional infrared absorption measurements.

The effect of oxygen exposure on pentacene electronic structure.

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O(2) and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O(2) at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.

Growth kinetics, structure, and morphology of para-quaterphenyl thin films on gold(111).

The adsorption, desorption, and growth kinetics as well as the thin film morphology and crystal structure of p-quaterphenyl (4P) grown under ultrahigh vacuum conditions on single crystalline Au(111) have been investigated. Thermal desorption spectroscopy (TDS) reveals two distinct first-order peaks attributed to monolayer desorption followed by a zero-order multilayer desorption. The saturation coverage of the full 4P monolayer has been quantitatively measured with a quartz microbalance to be 8 x 10(13) molecules/cm2. Using low energy electron diffraction the structures of the 0.5 and 1 ML (monolayer) adsorbates have been studied, showing highly regular arrangements of the 4P molecules, which are affected by the (111) surface structure. At the transition from 0.5 to 1 ML a structural compression of the overlayer has been observed. The behavior of thicker 4P films has been investigated by combined TDS-XPS (XPS-x-ray photoelectron spectroscopy). A temperature-induced recrystallization process at about 270 K has been observed for a 7 nm thick 4P film grown at 93 K, corresponding to a transition from a disordered layerlike growth to a crystalline island growth. Ex situ optical microscopy and atomic-force microscopy investigations have revealed needle-shaped 4P islands. Applying x-ray diffraction the crystalline order and epitaxial relationship of the 4P films with 30 nm and 200 nm mean thicknesses have been determined.