AFM studies on Langmuir-Blodgett films of cholesterol

The Langmuir monolayer of cholesterol at the air-water interface exhibits a condensed phase in which the cholesterol molecules are aligned normal to the water surface. We have transferred the monolayer from water surface to different substrates by Langmuir-Blodgett (LB) technique and have studied their assembly by atomic force microscope (AFM). Our studies reveal that the aggregation of cholesterol molecules on hydrophobic surfaces leads to interesting structures. The cholesterol molecules assemble into a uniform film, elongated domains and uniformly distributed torus-shaped domains (doughnuts) for one, two and four cycles of deposition, respectively. Beyond four cycles, the molecules adsorb and desorb by an equal amount resulting in no further deposition. The formation of uniformly distributed doughnuts can be attributed to the hydrophobic interaction and reorganization of the molecules due to successive adsorption and desorption during deposition cycles. Our studies on hydrophilic surfaces show that cholesterol cannot form more than one layer of deposition.PACS: 68.47.Pe Langmuir-Blodgett films on solids; polymers on surfaces; biological molecules on surfaces - 68.37.Ps Atomic force microscopy (AFM) - 68.43.Mn Adsorption/desorption kinetics     

Adsorption of hydrogen and hydrocarbon molecules on SiC(001)

Adsorption of hydrogen and hydrocarbon molecules on semiconductor surfaces plays a key role in surface science and technology. Most studies have employed silicon (Si) as a substrate because of its paramount technological importance and scientific interest. However, other semiconductor substrates are gaining an increasing interest as well. Silicon carbide (SiC), which is a material with very special properties allowing developments of novel devices and applications, offers particularly fascinating new degrees of freedom for exceptional adsorption behaviour. For example, a very unusual hydrogen-induced metallization of a SiC(001) surface has been reported and hydrogen molecules show very different adsorption behaviour on different SiC(001) reconstructions although the latter exhibit very similar surface dimers. In marked contrast to the Si(001) surface, the adsorption of hydrocarbon molecules on SiC(001) can yield structurally well-defined adlayers in favourable cases which may have large potential for organic functionalization. We review and discuss theoretical ab initio results on conceivable adsorption scenarios of atomic and molecular hydrogen as well as acetylene, ethylene, butadiene, benzene and cyclohexadiene on various reconstructions of the SiC(001) surface. The main emphasize is on a detailed understanding of these adsorption systems and on identifying the physical origin of the particular adsorption behaviour. The results will be discussed in the light of related adsorption events on the Si(001) surface and in comparison with available experimental data.     

Organic Surface Science: Creating Order And Complexity Using Self-Assembly

Surfaces of organic materials are receiving an increased attention since their physical and chemical properties can be tailored very specifically by the choice of an appropriate organic molecule. The fabrication of well-defined organic surfaces with a high degree of structural order, however, is not straightforward. In many cases the preferred route is to deposit organic molecules on a solid, inorganic substrate. The growth of soft matter, molecules, on hard matter, metals, semiconductors or insulators, however, requires a detailed understanding of the substrate-adlayer interaction on a molecular level. Here we will discuss typical problems encountered in the epitaxy of organic molecules on inorganic substrates. Some basic concepts are outlined and illustrated, with particular emphasis on the epitaxial growth of organic semiconductors relevant for making molecular electronics devices and on the formation of selfassembled organothiolate monolayers on metal surfaces.     

Statistical interpretation of the kinetic equation in the adsorption problem

A statistical interpretation for the adsorption phenomenon is presented in the framework of the Maxwell-Boltzmann statistics. A model for an adsorbing surface is proposed and the connection between the phenomenological parameters, entering in the kinetic equation at the boundary surfaces, with the microscopic model is derived.Received: 14 June 2004, Published online: 14 September 2004PACS: 66.10.-x Diffusion and ionic conduction in liquids - 68.43.-h Chemisorption/physisorption: adsorbates on surfaces - 68.43.Mn Adsorption/desorption kinetics     

Scanning tunneling spectroscopy and manipulation of C<Subscript>60</Subscript> on Cu(111)

The properties of C₆₀ adsorbed on Cu(111) have been studied using low temperature scanning tunnelling microscopy and spectroscopy. In the electronic spectrum of the molecule, we observe features that can be assigned to molecular orbitals. The LUMO level is split into two states, as a consequence of the charge transfer from the substrate to the carbon cage. The data from the inelastic electron tunnelling spectroscopy reveal two peaks that can be assigned to the intramolecular vibrational modes of the C₆₀ cage. We demonstrate also controlled manipulation of single molecules. The plot of the tip height, recorded during the manipulation process, indicates that the C₆₀ is pushed along the surface. PACS 68.37.Ef; 73.61.Wp; 68.43.Pq; 82.37.GK; 68.43.-h     

Calculation of conductance spectra of silver clusters on graphite

The transport properties of Ag_n clusters, 40<n< 100, deposited on crystalline graphite and probed with a tunneling tip are analyzed by using non-equilibrium Green’s functions. Current–voltage characteristics are computed accounting for self-consistent charge redistribution in the cluster caused by coupling to the surface and the external bias. The differential conductance is compared to the density of states of the supported clusters at equilibrium, highlighting the effects of charging and substrate properties on the measured spectrum. PACS 61.46.+w; 73.63.-b; 68.43.-h; 73.22.-f     

Multi-dimensional mixed quantum–classical description of the laser-induced desorption of molecules

A mixed quantum–classical method for the simulation of laser-induced desorption processes at surfaces is implemented. In this method, the nuclear motion is described classically, while the electrons are treated quantum mechanically. The feedback between nuclei and electrons is taken into account self-consistently. The computational efficiency of this method allows a more realistic multi-dimensional treatment of desorption processes. We apply this method to the laser-induced desorption of NO from NiO(100) using a two-state two-dimensional potential energy surface derived from ab initio quantum chemical calculations; we extend this potential energy surface to seven dimensions employing a physically reasonable model potential. By comparing our method to jumping wave-packet calculations on exactly the same potential energy surface we verify the validity of our method. We focus on the velocity, rotational, and vibrational distributions of the desorbing NO molecules. Furthermore, we model the energy transfer to the substrate by a surface oscillator. Including recoil processes in the simulation has a decisive influence on the desorption dynamics, as far as the velocity and rotational distribution is concerned. In particular, the bimodality in the velocity distribution observed in low dimensions and in the experiment disappears in a high-dimensional treatment. PACS  68.43.Tj; 68.43.Rs; 82.20.Gk; 82.20.Wt     

Anchoring of organic molecules to a metal surface: HtBDC on Cu(110)

The interaction of largish molecules with metal surfaces has been studied by combining the imaging and manipulation capabilities of the scanning tunneling microscope (STM). At the atomic scale, the STM results directly reveal that the adsorption of a largish organic molecule can induce a restructuring of a metal surface underneath. This restructuring anchors the molecules on the substrate and is the driving force for a self-assembly process of the molecules into characteristic molecular double rows.     

Adsorption of <Emphasis Type="Italic">d</Emphasis>-metal atoms on the regular MgO(001) surface: Density functional study of cluster models embedded in an elastic polarizable environment

Structure and bonding of complexes formed by 17 different single transition metal atoms (Cu, Ag, Au; Ni, Pd, Pt; Co, Rh, Ir; Fe, Ru, Os; Mn, Re; Cr, Mo, W) with oxygen sites of the regular MgO(001) surface were studied computationally. We employed an all-electron scalar-relativistic density functional method in combination with our novel scheme of cluster models embedded in an elastic polarizable environment that allows one to account for substrate relaxation. Even on a rigid substrate such as ideal MgO(001), adsorbate-induced relaxation noticeably affects structure and stability of surface complexes. For more reliable estimates, we calculated adsorption energies with two different gradient-corrected exchange-correlation functionals, BP86 and PBEN. More than one electron configuration was considered for metal atoms exhibiting high-spin states adsorption complexes. Within one group of the periodic table, 3d-atoms, in general, were found to adsorb more strongly than 4d-atoms, but weaker than 5d-atoms. In line with our previous studies of selected d-metal atoms adsorbed on oxides, the surface complexes considered did now show any indication of metal oxidation. PACS 68.43.Bc; 68.43.Fg; 71.15.Nc; 82.65.+r; 68.35.Ct; 68.43.-h; 73.20.Hb; 71.15.Mb; 75.70.Cn     

Optical anisotropy of cyclopentene terminated GaAs(001) surfaces

Up to now most of the experimental work regarding the adsorption of organic molecules has been concerned with silicon. Here we study the interface formation on a III–V-semiconductor, GaAs(001). We show that reflectance anisotropy spectroscopy (RAS) is a sensitive technique for investigating the interface formation between organic molecules and semiconductor surfaces. With RAS it is possible to determine the surface reconstruction and the structural changes at the interface during the deposition of organic molecules. These changes and the underlying adsorption process are discussed here for the adsorption of cyclopentene on GaAs(001)c(4×4), (2×4) and (4×2). PACS 61.66.Hq; 72.80.Le; 34.50.Dy; 68.47.Fg     

Low energy electron diffraction and auger electron spectroscopy studies of the structure of adsorbed gases on solid surfaces

Low energy electron diffraction (LEED) studies of the structure of adsorbed molecules on crystal surfaces revealed that ordered surface structures predominate under most conditions of the experiments. In the absence of chemical reactions with the substrate, the degree of ordering depends on the heats of adsorption, ΔH_ads, and the activation energies for surface diffusion, ΔE_D1. Since ΔH_ads is usually markedly larger than ΔE_D1, small changes of substrate temperature facilitate ordering without appreciable increase in desorption rates. The surface structures of adsorbed gases that have been reported so far have been tabulated. For molecules whose size is compatible with the interatomic distance of the substrate, rules of ordering can be proposed that permit prediction of the structure of the adsorbed layer that is likely to form. These rules indicate close packing due to attractive interactions in the adsorbed layer, and that the rotational multiplicity of the substrate is likely to be maintained by the adsorbate structure. When molecules whose dimensions are larger than the substrate interatomic distance are adsorbed, the conditions that control ordering are more complex and simple rules may not be readily applicable.The surface structures of adsorbed gases have also been studied on high Miller Index substrate surfaces. These surfaces are characterized by ordered steps separated by terraces of low index surface orientation. Many gases have different ordering characteristics on stepped surfaces than on low index crystal faces due to the stronger substrate-adsorbate interactions in these surfaces. The dissociation of diatomic molecules at steps induces the formation of new types of surface structures (frequently one-dimensional) and the dehydrogenation of hydrocarbons at steps induces the formation of ordered carbonaceous surface structures that would not nucleate on low index substrate planes.So far, mostly work function changes upon adsorption gave indication of the magnitude of charge transfer upon adsorption and on forming of new surface chemical bonds. Most recently, chemical shifts of the Auger transitions of the substrate atoms and of the adsorbed molecules upon chemisorption, have been found to provide additional information on charge redistribution during adsorption.     

Electronic,structural and chemical effects of charge-transfer at organic/inorganic interfaces

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical reactivity of the adsorbates. The aim of this review is to start drawing general conclusions and developing new concepts which will help the scientific community to proceed more efficiently towards the understanding of organic/inorganic interfaces in the strong interaction limit, where charge-transfer effects must be taken into consideration.     

Attracted by long-range electron correlation: adenine on graphite

The adsorption of adenine on graphite is analyzed from first-principles calculations as a model case for the interaction between organic molecules and chemically inert surfaces. Within density-functional theory we find no chemical bonding due to ionic or covalent interactions, only a very weak attraction at distances beyond the equilibrium position due to the lowering of the kinetic energy of the valence electrons. Electron exchange and correlation effects are much more important for the stabilization of the adsystem. They are modeled by the local density or generalized gradient approximation supplemented by the London dispersion formula for the van der Waals interaction.     

STM analysis of triosmium carbonyl cluster adsorption at HOPG

The study of metallic carbonyl clusters as precursors in tailoring the heterogeneous metal catalysts has been of great importance. The catalytic nature of the adsorbed clusters in thin film form depends on the chemical properties of the substrate used. The metal-support interaction will determine various properties such as the surface morphology, adsorption features and the structural orientations. We report a scanning tunneling microscopy (STM) study of an osmium carbonyl cluster (Os₃(CO)₁₁(NCCH₃)) adsorbed on highly oriented pyrolytic graphite (HOPG). STM measurements showed that the osmium carbonyl cluster interacts with HOPG in such a way that it adsorbs on the basal plane showing regular lattice structure, whereas the axial planes of the HOPG surface shows no ordered structure. The regular cluster lattice structure of the carbonyl cluster on the basal plane of the graphite has lattice parameters of a=1.4 nm and b=1.5 nm. We believe that the regular orientation of the cluster indicates a monolayer adsorption of the cluster on the graphite basal planes. Scanning tunneling spectroscopy (STS) measurements also indicated an insulating behavior for the cluster molecules on HOPG, with a significant energy gap value of ca. 300 mV. The cluster interaction at the active sites, i.e. axial planes of the graphite, was also observed by in situ STM measurements.     

Adsorption and organisation of para-hexaphenyl molecules on Si(100)

Para-hexaphenyl molecules (p-6P: C₃₆H₂₆) can be grown as nanofibres on various surfaces having optical properties of technological relevance. We report here the first observations of the initial stages of adsorption of individual p-6P molecules on Si(100)-(2×1) using room temperature Scanning Tunnelling Microscopy (STM). Depending on the substrate temperature, the hexaphenyl molecules adsorb in two configurations; indicating both weak and strong chemisorption. All six phenyl rings are clearly visible and the molecules are found to adsorb with characteristic angles between the long axis of the molecule and the silicon dimer rows. A statistical analysis of the spatial distribution of the molecules suggests that the clustering required for crystallographic nanofibre growth does not occur at the atomic scale under the experimental conditions used here.     

In situ electrochemical scanning tunneling microscopy investigation of renewing graphite surface accompanied by electrochemical reaction

In situ electrochemical scanning tunneling microscopy (ECSTM) has been employed to follow the renewal process of a graphite electrode accompanied by flavin adenine dinucleotide (FAD) electrochemical reaction which involves adsorption of the reduced form (FADH₂) and desorption of the oxidized form (FAD). The renewal process initiates from steps or kinks on the electrode surface, which provide high active sites for adsorption. This renewal depends on the working electrode potential, especially in the range near the FAD redox potential. Our experiment suggests that delamination of the graphite surface is caused by interaction between the substrate and adsorbed molecules. A simple model is proposed to explain this phenomenon.     

Luminescence of molecules adsorbed on surfaces of wide gap materials

We report on the photoluminescence spectra of thin films of chain-like π-conjugated molecules on well-defined surfaces of wide gap inorganic materials. The aim is to study the energy transfer processes across the organic/substrate interface which limit the luminescence of molecules in close contact to substrate surfaces. We discuss quaterthiophene (4 T) adsorbed on the c(2×2)-ZnSe(0 0 1) surface and tetracene (Tc) on the surface of a thin epitaxial Al₂O₃ film on Ni₃Al(1 1 1). For thin films vapor-deposited at low substrate temperatures, we observe no luminescence signal for both systems, which indicates the presence of fast luminescence quenching processes at the organic/inorganic interface. After annealing, luminescence spectra corresponding to those of the bulk crystals are obtained. This can be explained by the formation of 3D-crystallites, which effectively separate most molecules from the organic/inorganic interface.     

Adsorption of oxygen on Si(100) steps: a study at semiempirical level

In this study oxygen adsorption on steps of the Si(100) surface is investigated with quantum mechanical detail. A cluster model represents the step structure and the oxygen impurity is deposited in this cluster above the dimer rows. A map of the total energy sensed by the adsorbate is constructed by displacing the oxygen atom on the terraces and down the step and allowing the system to relax to the total-energy-optimized configuration by a steepest-descent method. A self-consistent semiempirical molecular orbital method is applied to the evaluation of the total energy. Though the adsorption geometries are reminiscent of the ones observed for the flat surface, the effects of the step geometry are noticeable. They influence both the preferred adsorption sites and the properties of the electronic configuration of the adsorbed system.Received: 24 July 2003, Published online: 22 September 2003PACS: 68.43.Fg Adsorbate structure (binding sites, geometry) - 68.90.+g Other topics in structure, and nonelectronic properties of surfaces and interfaces; thin films and low-dimensional structures (restricted to new topics in section 68) - 07.05.Tp Computer modeling and simulation     

A simple swelling and anchoring method for preparing dense and stable poly(ethylene oxide) layers on polystyrene surfaces

In order to obtain dense and stable poly(ethylene oxide) (PEO) layers for reducing protein adsorption, polystyrene (PS) plates were first soaked in chloroform/methanol mixed organic solvent to swell the polymer. The swelled PS plates were then immersed into Pluronic F127 (amphiphilic block copolymer) aqueous solution, Pluronic F127 molecules were adsorbed favorably on the swelled PS surfaces. After evaporation of organic solvent, the adsorbed Pluronic F127 molecules were trapped and anchored permanently on the PS substrates. The dense and stable PEO layers anchored on the PS surfaces can effectively inhibit protein adsorption.     

Complex formation and proton transfer between formic acid and water adsorbed on Au(111) surfaces under UHV conditions

The coadsorption of formic acid and water on Au(111) surfaces has been investigated by means of vibrational and photoelectron spectroscopy (HREELS, XPS). Formic acid adsorbs at 90 K molecularly with vibrational modes characteristic for flat lying zig-zag chains in the mono- and multilayer regime, like in solid formic acid. Annealing results in a complete desorption at 190 K. Sequential adsorption of formic acid and water at 90 K shows no significant chemical interaction. Upon annealing the coadsorbed layer to 140 K a hydrogen-bonded cyclic complex of formic acid with one water molecule could be identified using isotopically labelled adsorbates (D₂O, H¹³COOD). Upon further annealing this complex decomposes leaving molecularly adsorbed formic acid on the surface at 160 K, accompanied by a proton exchange between formic acid and water. PACS 68.08.-p; 68.43.-h; 68.43.Pq