Phase diagram of pentacene growth on Au(110)

We studied the growth of pentacene (C22H14) on the Au(110) surface by means of He atom scattering and Synchrotron X-ray photoemission. We found that two-dimensional commensurate growth only occurs in the monolayer range for a substrate temperature, T(s), higher than approximately 370 K. Larger amounts of deposited molecules forms three-dimensional uncorrelated clusters on the wetting layer. The desorption of second layer molecules occurs at T(s) > or = 420 K. The highest coverage ordered phase displays a (6 x 8) symmetry and corresponds to the saturation coverage at T(s) = 420 K. The (3 x 6) symmetry phase, recently reported for a multilayer planar film [Ph. Guaino, et al. Appl. Phys. Lett. 2004, 85, 2777], is only found at a coverage slightly lower than the (6 x 8) one. The (3 x 6) phase corresponds to the saturation coverage of the first layer at T(s) = 470 K.     

Amino-carboxylic recognition on surfaces: from 2D to 2D + 1 nano-architectures

The control of the electronic properties of the interfaces between small organic molecules and the substrate is key for the development of efficient and reliable organic-based devices. A promising and widely covered route is to interpose a Self-Assembled Monolayer (SAM) to bridge the molecular film and the electrode. The morphology and the electronic level alignment of the triple substrate-SAM-organic layered system can be tuned by properly selecting the SAM composition. We have recently proposed a novel approach to the problem where, under ultra-high vacuum conditions, a molecular film is anchored to the SAM by exploiting the recognition between molecules functionalized, respectively, with -NH(2) and -COOH end-groups. Here we briefly review the role of the amino-carboxylic interaction in the formation of ordered organic 2-dimensional architectures on solid surfaces. We then describe the anchoring process of carboxylic molecules on amine based SAMs we have recently reported on. New results are presented showing how multiple anchoring sites per molecule may be exploited for tailoring the molecular orientation as well as the density of the anchored molecules.     

Ionization energy and energy gap structure of MoSI molecular wires: Kelvin probe, ultraviolet photoelectron spectroscopy, and cyclic voltammetry measurements

The work function W of Mo(6)S(3)I(6) molecular nanowires is determined by Kelvin probe (KP) measurements, UV photoelectron spectroscopy (UPS), and cyclic voltammetry (CV). The values obtained by all three methods agree well, giving W = 4.8 ± 0.1 eV. CV measurements also give a gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of E(g) = 1.2 ± 0.1 eV, in agreement with recent optical measurements, but in disagreement with theoretical calculations, which predict the material to be a metal. The electronic structure of Mo(6)S(3)I(6) suggests use of the material in applications such as bulk heterostructure photovoltaics and transparent electrodes and for molecular electronics devices.     

Phase and structural order in mixture of nematic liquid crystals and anisotropic nanoparticles

We studied the structural order in randomly perturbed nematic liquid crystals using a random anisotropic nematic-type lattice model. Simulations were carried out at zero temperature and at various other temperatures, for which we varied the concentration of impurities p, anchoring strength W and imposed external strength fields B at two different histories: temperature-quenched history (TQH) and field-quenched history. The Haller approximation method utilized the temperature dependence of the order parameter to determine the pseudo-critical exponent β at different values of p and W. Consequently, the values of β increased when p and W were increased. Additionally, applying an external field B for investigating the parameters revealed that the TQH established long-range order for high magnitudes of B at zero temperature (T* = 0) and T* = 0.5.     

Random nematic structures in the absence of inherent frustrations

We study the impact of anisotropic nanoparticles (NPs) on the nematic liquid crystal (LC) order. Within a mesoscopic Flory–Huggins-type approach we have estimated regimes where LC–NP mixtures are essentially homogenous. Using a lattice Lebwohl–Lasher type approach we have also studied the impact of anisotropic NPs on LC ordering. We analysed the cases where the orientations of NPs are either frozen-in or could be varied, to which we refer as random field mixtures and annealed mixtures, respectively. In the latter case we have demonstrated the existence of qualitatively different regimes. In particular, we determined the concentration regime, where LC configurations resembling a transparent nematic phase could be observed. Such domain patterns are stabilised by NPs hindering the annihilation of topological defects in LC order.     

Electronic and geometric characterization of the L-cysteine paired-row phase on Au(110)

We have studied the vapor-phase deposition of L-cysteine on the Au(110) surface by means of synchrotron-based techniques. Relying on a comparison with previous X-ray photoemission analysis, we have assigned the fine structure of the C K-shell X-ray absorption spectra to the nonequivalent carbon bonds within the molecule. In particular, the C1s --> sigma* transition, where the sigma* state is mainly localized on the C-S bond, is shifted well below the ionization threshold, at approximately -5 eV from the characteristic pi* transition line related to carboxylic group. From the polarization dependence of the absorption spectra in the monolayer coverage range, the molecules are found to lay flat on the surface with both the C-S bond and the carboxylic group almost parallel to the surface. We performed in situ complementary surface X-ray diffraction, SXRD, measurements to probe the rearrangement of the Au atoms beneath the L-cysteine molecules. Since the early stage of deposition, L-cysteine domains are formed which display an intermediate fourfold symmetry along [001]. The self-assembly of molecules into paired rows, extending along the [1(-)10] direction, is fully compatible with our observations, as has been reported for the case of D-cysteine molecules grown on Au(110) [Kühnle, A. et al. Phys. Rev. Lett. 2004, 93, 086101.]     

Heterostructured organic interfaces probed by resonant photoemission

The application of the resonant photoemission spectroscopy (RPES) to various organic molecule based systems is reviewed. The chemical specificity and the possibility to conduct experiments in the energy domain that provides a time scale for charge dynamics, make the RPES a powerful tool to study organic heterojunctions and in particular to probe the charge transfer processes at organic interfaces. We briefly discuss the models used in RPES data analysis to extract the time scale of the excited charge delocalisation and the spatial correlation of core, valence occupied and unoccupied molecular states. As an example we report on 3,4,9,10-perylene tetracarboxylic acid dianhydride (PTCDA) on (1 × 2) Au(1 1 0) surface where organic layer metallicity is directly evidenced in RPES experiments. A particular attention is dedicated to bio-mimetic model molecules whose electronic structure at interfaces is the fundamental key for the design of real devices. In the last section we consider recent experiments that could open the way to new fields of applications regarding biological molecules and single molecule systems where RPES could elucidate the link between the quantum and the meso-scopic properties of such systems.     

Atomically resolved images from near node photoelectron holography experiments on Al(111)

Sz?ke's concept for electron holography is hampered by forward scattering that dominates electron diffraction from electron point sources below the surface top layer. Forward scattering was proposed to be suppressed if the anisotropic nature of the electron source wave is exploited [T. Greber and J. Osterwalder, Chem. Phys. Lett. 256, 653 (1996)]. Experiments show a strong suppression of forward scattering in Al(111) if Al 2s photoelectrons (E(kin) = 952 eV) are measured near the nodal plane of the outgoing p wave. The holographic reconstruction from such diffraction data provides three dimensional images of atomic sites in unit cells with a size of more than 10 A.     

Length‐Independent Charge Transport in Chimeric Molecular Wires

Advanced molecular electronic components remain vital for the next generation of miniaturized integrated circuits. Thus, much research effort has been devoted to the discovery of lossless molecular wires, for which the charge transport rate or conductivity is not attenuated with length in the tunneling regime. Herein, we report the synthesis and electrochemical interrogation of DNA‐like molecular wires. We determine that the rate of electron transfer through these constructs is independent of their length and propose a plausible mechanism to explain our findings. The reported approach holds relevance for the development of high‐performance molecular electronic components and the fundamental study of charge transport phenomena in organic semiconductors.     

Ultrahigh vacuum deposition of L-cysteine on Au(110) studied by high-resolution X-ray photoemission: from early stages of adsorption to molecular organization

We report on a high-resolution X-ray photoemission spectroscopy study on molecular-thick layers of L-cysteine deposited under ultrahigh vacuum conditions on Au(110). The analysis of core level shifts allowed us to distinguish unambiguously the states of the first-layer molecules from those of molecules belonging to the second layer. The first-layer molecules strongly interact with the metal through their sulfur headgroup. The multipeaked structure of the N 1s, O 1s, and C 1s core levels is interpreted in terms of different molecular moieties. The neutral acidic fraction (HSCH2CH(NH2)COOH) is abundant at low coverage likely associated with isolated molecules or dimers. The zwitterionic phase (HSCH2CH(NH3+)COO-) is largely dominant as the coverage approaches the monolayer limit and is related to the formation of ordered self-assembled molecular structures indicated by electron diffraction patterns. The occurrence of a small amount of cationic molecules (HSCH2CH(NH3+)COOH) is also discussed. The second-layer molecules mainly display zwitterionic character and are weakly adsorbed. Mild annealing up to 100 degrees C leads to the desorption of the second-layer molecules leaving electronic states of the first layer unaltered.