Odd-even effects in the structure and properties of aryl-substituted aliphatic self-assembled monolayers

Self-assembled monolayers (SAMs) represent an important tool in context of nanofabrication and molecular engineering of surfaces and interfaces. The properties of functional SAMs depend not only on the character of the tail groups at the SAM-ambient interface, but are also largely defined by their structure. In its turn, the latter parameter results from a complex interplay of the structural forces and a variety of other factors, including so called odd-even effects, viz. dependence of the SAM structure and properties on the parity of the number (odd or even) of individual building blocks in the backbone of the SAM constituents. The most impressive manifestation of the odd-even effects is the structure of aryl-substituted alkanethiolate SAMs on Au(111) and Ag(111), in which, in spite of the fact that the intermolecular interaction is mostly determined by the aryl part of the monolayers, one observes a pronounced dependence of molecular inclination and, consequently, the packing density of the SAM-forming molecules on the parity of number of methylene units in the alkyl linker. Here we review the properties of the above systems as well as address fundamental reasons behind the odd-even effects, including the existence of a so-called bending potential, which is frequently disregarded in analysis of the structure-building forces. The generality of the odd-even effects in SAMs is additionally supported by the recent data for SAMs on GaAs, scanning tunneling microscopy data for SAMs on Ag(111), and the data for the monolayers with selenolate and carboxyl anchoring groups on Au(111) and Ag(111). The implications of these effects in terms of the control over the packing density and orientation of the tail groups at the SAM-ambient interface, structural perfection, polymorphism, temperature-driven phase transitions, and SAM stability toward such factors as ionizing radiation, exchange reaction, and electrochemical desorption are discussed. These implications place the odd-even effects as an important tool for the design of functional SAMs in context of specific applications

Universality for 2D Wedge Wetting

We study 2D wedge wetting using a continuum interfacial Hamiltonian model which is solved by transfer-matrix methods. For arbitrary binding potentials, we are able to exactly calculate the wedge free-energy and interface height distribution function and, thus, can completely classify all types of critical behaviour. We show that critical filling is characterized by strongly universal fluctuation dominated critical exponents, whilst complete filling is determined by the geometry rather than fluctuation effects. Related phenomena for interface depinning from defect lines in the bulk are also considered.Comment: 4 pages, 1 figur

Three dimensional tracking of exploratory behavior of barnacle cyprids using stereoscopy

Surface exploration is a key step in the colonization of surfaces by sessile marine biofoulers. As many biofouling organisms can delay settlement until a suitable surface is encountered, colonization can comprise surface exploration and intermittent swimming. As such, the process is best followed in three dimensions. Here we present a low-cost transportable stereoscopic system consisting of two consumer camcorders. We apply this novel apparatus to behavioral analysis of barnacle larvae (? 800 lm length) during surface exploration and extract and analyze the three-dimensional patterns of movement. The resolution of the system and the accuracy of position determination are characterized. As a first practical result, three-dimensional swimming trajectories of the cypris larva of the barnacle Semibalanus balanoides are recorded in the vicinity of a glass surface and close to PEG2000-OH and C11NMe3 +Cl- terminated self-assembled monolayers. Although less frequently used in biofouling experiments due to its short reproductive season, the selected model species [Marechal and Hellio (2011), Int Biodeterior Biodegrad, 65(1):92-101] has been used following a number of recent investigations on the settlement behavior on chemically different surfaces [Aldred et al. (2011), ACS Appl Mater Interfaces, 3(6):2085-2091]. Experiments were scheduled to match the availability of cyprids off the north east coast of England so that natural material could be used. In order to demonstrate the biological applicability of the system, analysis of parameters such as swimming direction, swimming velocity and swimming angle are performed.DFG/Ro 2524/2-2DFG/Ro 2497/7-2ONR/N00014-08-1-1116ONR/N00014-12-1-0498EC/FP7/2007-2013/23799

The Effects of Embedded Dipoles in Aromatic Self-Assembled Monolayers

Using a representative model system, here electronic and structural properties of aromatic self-assembled monolayers (SAMs) are described that contain an embedded, dipolar group. As polar unit, pyrimidine is used, with its orientation in the molecular backbone and, consequently, the direction of the embedded dipole moment being varied. The electronic and structural properties of these embedded-dipole SAMs are thoroughly analyzed using a number of complementary characterization techniques combined with quantum-mechanical modeling. It is shown that such mid-chain-substituted monolayers are highly interesting from both fundamental and application viewpoints, as the dipolar groups are found to induce a potential discontinuity inside the monolayer, electrostatically shifting the core-level energies in the regions above and below the dipoles relative to one another. These SAMs also allow for tuning the substrate work function in a controlled manner independent of the docking chemistry and, most importantly, without modifying the SAM-ambient interface

Exchange Reactions between Alkanethiolates and Alkaneselenols on Au{111}

When alkanethiolate self-assembled monolayers on Au{111} are exchanged with alkaneselenols from solution, replacement of thiolates by selenols is rapid and complete, and is well described by perimeter-dependent island growth kinetics. The monolayer structures change as selenolate coverage increases, from being epitaxial and consistent with the initial thiolate structure to being characteristic of selenolate monolayer structures. At room temperature and at positive sample bias in scanning tunneling microscopy, the selenolate-gold attachment is labile, and molecules exchange positions with neighboring thiolates. The scanning tunneling microscope probe can be used to induce these place-exchange reactions

Concept of Embedded Dipoles as a Versatile Tool for Surface Engineering

[Image: see text] Controlling the physical and chemical properties of surfaces and interfaces is of fundamental relevance in various areas of physical chemistry and a key issue of modern nanotechnology. A highly promising strategy for achieving that control is the use of self-assembled monolayers (SAMs), which are ordered arrays of rodlike molecules bound to the substrate by a suitable anchoring group and carrying a functional tail group at the other end of the molecular backbone. Besides various other applications, SAMs are frequently used in organic electronics for the electrostatic engineering of interfaces by controlling the interfacial level alignment. This is usually achieved by introducing a dipolar tail group at the SAM–semiconductor interface. Such an approach, however, also changes the chemical character of that interface, for example, affecting the growth of subsequent layers. A strategy for avoiding this complication is to embed polar groups into the backbones of the SAM-forming molecules. This allows disentangling electronic interface engineering and the nucleation of further layers, such that both can be optimized independently. This novel concept was successfully demonstrated for both aliphatic and aromatic SAMs on different application-relevant substrates, such as gold, silver, and indium tin oxide. Embedding, for example, ester and pyrimidine groups in different orientations into the backbones of the SAM-forming molecules results in significant work-function changes. These can then be fine-tuned over a wide energy range by growing mixed monolayers consisting of molecules with oppositely oriented polar groups. In such systems, the variation of the work function is accompanied by pronounced shifts of the peaks in X-ray photoelectron spectra, which demonstrates that electrostatically triggered core-level shifts can be as important as the well-established chemical shifts. This illustrates the potential of X-ray photoelectron spectroscopy (XPS) as a tool for probing the local electrostatic energy within monolayers and, in systems like the ones studied here, makes XPS a powerful tool for studying the composition and morphology of binary SAMs. All these experimental observations can be rationalized through simulations, which show that the assemblies of embedded dipolar groups introduce a potential discontinuity within the monolayer, shifting the energy levels above and below the dipoles relative to each other. In molecular and monolayer electronics, embedded-dipole SAMs can be used to control transition voltages and current rectification. In devices based on organic and 2D semiconductors, such as MoS(2), they can reduce contact resistances by several orders of magnitude without adversely affecting film growth even on flexible substrates. By varying the orientation of the embedded dipolar moieties, it is also possible to build p- and n-type organic transistors using the same electrode materials (Au). The extensions of the embedded-dipole concept from hybrid interfaces to systems such as metal–organic frameworks is currently underway, which further underlines the high potential of this approach