Luca Floreano

Tuning the catalytic activity of Ag(110)-supported Fe phthalocyanine in the oxygen reduction reaction.

A careful choice of the surface coverage of iron phthalocyanine (FePc) on Ag (110) around the single monolayer allows us to drive with high precision both the long-range supramolecular arrangement and the local adsorption geometry of FePc molecules on the given surface. We show that this opens up the possibility of sharply switching the catalytic activity of FePc in the oxygen reduction reaction and contextual surface oxidation in a reproducible way. A comprehensive and detailed picture built on diverse experimental evidence from scanning tunnelling microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy, coupled with density functional theory calculations, sheds new light on the nature of the catalytically active molecule-surface coordination and on the boundary conditions for its occurrence. The results are of relevance for the improvement of the catalytic efficiency of metallo-macrocycles as viable substitutes for platinum in the cathodic compartment of low-temperature fuel cells.

High resolution X-ray photoelectron spectroscopy of L-cysteine self-assembled films

The increasing demand for heterogeneous materials prompts the interest for the physics and chemistry of organic–inorganic interfaces. Within this field of interest we have investigated the electronic states of L-cysteine (Cys) adsorbed on Au(111) from aqueous solution with synchrotron-based, high resolution X-ray photoemission spectroscopy. The analysis of the S 2p core level region in pristine samples prepared with purified Cys indicates that Cys adsorbs on gold as a thiolate. The absence of a signal related to physisorbed sulfur indicates that Cys forms a monomolecular layer. The high resolution allowed us to resolve two components in the C 1s spectral region related to carboxyl. The comparative analysis of C 1s, N 1s and O 1s core level regions indicates the presence of the neutral and ionic form for both the carboxyl and the amine groups. From the quantitative analysis of the C 1s and N 1s data we can infer that the zwitterionic form is the prevalent one, with a ratio of zwitterionic to neutral molecules of 3∶1. This value is quite different from that in the deposition solution. Prolonged exposure to the X-ray beam and thermal annealing induce the formation of atomic sulfur through S–C bond breaking and molecular fragment desorption. This response to X-ray irradiation differs from the results recently reported on long chain alkanethiols.

Understanding energy-level alignment in donor-acceptor/metal interfaces from core-level shifts

The molecule/metal interface is the key element in charge injection devices. It can be generally defined by a monolayer-thick blend of donor and/or acceptor molecules in contact with a metal surface. Energy barriers for electron and hole injection are determined by the offset from HOMO (highest occupied) and LUMO (lowest unoccupied) molecular levels of this contact layer with respect to the Fermi level of the metal electrode. However, the HOMO and LUMO alignment is not easy to elucidate in complex multicomponent, molecule/metal systems. We demonstrate that core-level photoemission from donor-acceptor/metal interfaces can be used to straightforwardly and transparently assess molecular-level alignment. Systematic experiments in a variety of systems show characteristic binding energy shifts in core levels as a function of molecular donor/acceptor ratio, irrespective of the molecule or the metal. Such shifts reveal how the level alignment at the molecule/metal interface varies as a function of the donor-acceptor stoichiometry in the contact blend.

Quantifying through-space charge transfer dynamics in π-coupled molecular systems

Understanding the role of intermolecular interaction on through-space charge transfer characteristics in π-stacked molecular systems is central to the rational design of electronic materials. However, a quantitative study of charge transfer in such systems is often difficult because of poor control over molecular morphology. Here we use the core-hole clock implementation of resonant photoemission spectroscopy to study the femtosecond charge-transfer dynamics in cyclophanes, which consist of two precisely stacked π-systems held together by aliphatic chains. We study two systems, [2,2]paracyclophane (22PCP) and [4,4]paracyclophane (44PCP), with inter-ring separations of 3.0 and 4.0 Å, respectively. We find that charge transfer across the π-coupled system of 44PCP is 20 times slower than in 22PCP. We attribute this difference to the decreased inter-ring electronic coupling in 44PCP. These measurements illustrate the use of core-hole clock spectroscopy as a general tool for quantifying through-space coupling in π-stacked systems.

High resolution XPS of the S?2p core level region of the L-cysteine/gold interface

L-cysteine self-assembled monolayers (SAMs) have been deposited on gold from the liquid and vapour phase. Synchrotron based high resolution x-ray photoemission spectroscopy has been used to characterize the sulfur chemical states at the SAM/gold interface. Results obtained from pristine and x-ray irradiated samples, prepared with both as-received and purified L-cysteine, are reported. Pristine samples prepared with purified cysteine are characterized by an intense, largely dominant S 2p state at a binding energy around 162 eV (2p3/2 level) assigned to thiolates. A second doublet around 161 eV develops during irradiation. By comparison with the literature, this doublet is assigned to atomic sulfur present either as impurity or generated by S–C bond scission. Comparative measurements performed, under similar experimental conditions, on pristine 3-mercaptopropionic acid [HS(CH2)2COOH] layers deposited from the liquid phase are also presented and discussed.

Supramolecular Engineering through Temperature-Induced Chemical Modification of 2H-Tetraphenylporphyrin on Ag(111): Flat Phenyl Conformation and Possible Dehydrogenation Reactions

Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation.

Electronic states of CuPc chains on the Au(110) surface

The electronic properties of Cu-phthalocyanine (CuPc) molecules flat lying along the channels of the Au(110) reconstructed surface have been investigated by means of ultraviolet and x-ray photoelectron spectroscopy. The ordered chains give rise to a highly ordered single-layer structure with a (5x3) symmetry. Although from the core-level analysis not any significant charge transfer between the molecules and the underlying Au surface is observed, the valence band photoemission data bring to light CuPc-induced features localized at the interface. In particular, energy versus momentum dispersion of an interface state reveals a bandwidth of about 90 meV along the enlarged Au channels, where the CuPc chains are formed, with a defined fivefold symmetry well fitting the CuPc intermolecular distance.

Mesoscopic donor-acceptor multilayer by ultrahigh-vacuum codeposition of Zn-tetraphenyl-porphyrin and C70.

The peculiar electrochemical and photophysical properties of porphyrin and fullerene molecules make them promising candidates for the construction of two- and three-dimensional organic-based materials. An important question is how pristine fullerene and porphyrin will organize when deposited on surfaces via in vacuum molecular beam evaporation. Here we show that codeposition of C(70) and Zn-tetraphenyl-porphyrin (ZnTPP) induces the self-assembly of electron-rich flat aromatic molecules at the curved surface of C(70), thus enhancing the chromophore interaction and forming a supramolecular multilayer donor-acceptor structure. While the ground-state electronic spectra almost reflect a simple summation of ZnTPP and C(70) components, the excited-state electrons at the porphyrin macrocycle can rapidly delocalize to the fullerene. The excited charge transfer time scale is faster than 1-2 fs, as shown by resonant photoemission for the core-excited charges.

The ALOISA end station at Elettra: a novel multicoincidence spectrometer for angle resolved APECS

Abstract Coincidence measurements have been extensively performed in atomic and molecular physics since early 1970s. To apply this methodology to solids and surfaces has been a major target since early days, but the long average time needed to complete a coincidence experiment has hampered its attainment. In particular the coincidence technique has not been yet applied in an angle resolved way such for studying the momentum correlation in the ejection of electron pairs from solid surfaces. The experimental chamber at the ALOISA beamline at Elettra, by means of a set of seven homemade electron analyzers, is the first apparatus able to perform Angle Resolved – Auger Photoelectron Coincidence Spectroscopy (AR-APECS) from solid surfaces. In the typical setup ten different pairs of coincident electrons can be measured simultaneously, so reducing the acquisition time by one order of magnitude.

Understanding charge transfer in donor-acceptor/metal systems: A combined theoretical and experimental study

We develop an effective potential approach for assessing the flow of charge within a two-dimensional donor-acceptor/metal network based on core-level shifts. To do so, we perform both density functional theory (DFT) calculations and x-ray photoemission spectroscopy (XPS) measurements of the core-level shifts for three different monolayers adsorbed on a Ag substrate. Specifically, we consider perfluorinated pentacene (PFP), copper phthalocyanine (CuPc) and their 1:1 mixture (PFP+CuPc) adsorbed on Ag(111).