Steven L. Tait

Chemically homogeneous and thermally reversible oxidation of epitaxial graphene

With its exceptional charge mobility, graphene holds great promise for applications in next-generation electronics. In an effort to tailor its properties and interfacial characteristics, the chemical functionalization of graphene is being actively pursued. The oxidation of graphene via the Hummers method is most widely used in current studies, although the chemical inhomogeneity and irreversibility of the resulting graphene oxide compromises its use in high-performance devices. Here, we present an alternative approach for oxidizing epitaxial graphene using atomic oxygen in ultrahigh vacuum. Atomic-resolution characterization with scanning tunnelling microscopy is quantitatively compared to density functional theory, showing that ultrahigh-vacuum oxidization results in uniform epoxy functionalization. Furthermore, this oxidation is shown to be fully reversible at temperatures as low as 260 °C using scanning tunnelling microscopy and spectroscopic techniques. In this manner, ultrahigh-vacuum oxidation overcomes the limitations of Hummers-method graphene oxide, thus creating new opportunities for the study and application of chemically functionalized graphene.

Charge-transfer-induced structural rearrangements at both sides of organic/metal interfaces

Organic/metal interfaces control the performance of many optoelectronic organic devices, including organic light-emitting diodes or field-effect transistors. Using scanning tunnelling microscopy, low-energy electron diffraction, X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure spectroscopy and density functional theory calculations, we show that electron transfer at the interface between a metal surface and the organic electron acceptor tetracyano-p-quinodimethane leads to substantial structural rearrangements on both the organic and metallic sides of the interface. These structural modifications mediate new intermolecular interactions through the creation of stress fields that could not have been predicted on the basis of gas-phase neutral tetracyano-p-quinodimethane conformation.

Self-recognition and self-selection in multicomponent supramolecular coordination networks on surfaces

Self-recognition, self-selection, and dynamic self-organization are of fundamental importance for the assembly of all supramolecular systems, but molecular-level information is not generally accessible. We present direct examples of these critical steps by using scanning tunneling microscopy to study mixtures of complementary organic ligands on a copper substrate. The ligands coordinate cooperatively with iron atoms to form well ordered arrays of rectangular multicomponent compartments whose size and shape can be deliberately tuned by selecting ligands of desired length from complementary ligand families. We demonstrate explicitly that highly ordered supramolecular arrays can be produced from redundant ligand mixtures by molecular self-recognition and -selection, enabled by efficient error correction and cooperativity, and show an example of failed self-selection due to error tolerance in the ligand mixture, leading to a disordered structure.

Spin and Orbital Magnetic Moment Anisotropies of Monodispersed Bis(Phthalocyaninato)Terbium on a Copper Surface

The magnetic properties of isolated TbPc(2) molecules supported on a Cu(100) surface are investigated by X-ray magnetic circular dichroism at 8 K in magnetic fields up to 5 T. The crystal field and magnetic properties of single molecules are found to be robust upon adsorption on a metal substrate. The Tb magnetic moment has Ising-like magnetization; XMCD spectra combined with multiplet calculations show that the saturation orbital and spin magnetic moment values reach 3 and 6 mu(B), respectively.

n-alkanes on Pt(111) and on C(0001)∕Pt(111): Chain length dependence of kinetic desorption parameters

We have measured the desorption of seven small n-alkanes (C(N)H(2N+2), N=1-4,6,8,10) from the Pt(111) and C(0001) surfaces by temperature programed desorption. We compare these results to our recent study of the desorption kinetics of these molecules on MgO(100) [J. Chem. Phys. 122, 164708 (2005)]. There we showed an increase in the desorption preexponential factor by several orders of magnitude with increasing n-alkane chain length and a linear desorption energy scaling with a small y-intercept value. We suggest that the significant increase in desorption prefactor with chain length is not particular to the MgO(100) surface, but is a general effect for desorption of the small n-alkanes. This argument is supported by statistical mechanical arguments for the increase in the entropy gain of the molecules upon desorption. In this work, we demonstrate that this hypothesis holds true on both a metal surface and a graphite surface. We observe an increase in prefactor by five orders of magnitude over the range of n-alkane chain lengths studied here. On each surface, the desorption energies of the n-alkanes are found to increase linearly with the molecule chain length and have a small y-intercept value. Prior results of other groups have yielded a linear desorption energy scaling with chain length that has unphysically large y-intercept values. We demonstrate that by allowing the prefactor to increase according to our model, a reanalysis of their data resolves this y-intercept problem to some degree.

n-alkanes on MgO(100). II. Chain length dependence of kinetic desorption parameters for small n-alkanes

Coverage-dependent desorption-kinetics parameters are obtained from high-quality temperature-programmed desorption data for seven small n-alkane molecules on MgO(100). The molecules, CNH2N+2 (N=1-4,6,8,10), were each studied for a set of 29 initial coverages at a heating ramp rate of 0.6 K/s as well as at a set of nine ramp rates in the range of 0.3-10.0 K/s. The inversion analysis method with its least-squares preexponential factor (prefactor) optimization discussed in the accompanying article is applied to these data. This method allows for accurate determination of prefactors and coverage-dependent desorption energies. The prefactor for desorption increases dramatically with chain length from 10(13.1) to 10(19.1) s(-1) over the range of N=1-10. We show that this increase can be physically justified by considering the increase in rotational entropy available to the molecules in the gaslike transition state for desorption. The desorption energy increases with chain length as Ed(N)=6.5+7.1N, which implies an incremental increase of 7.1+/-0.2 kJ/mol per CH2.

Metal-organic coordination interactions in Fe-Terephthalic acid networks on Cu(100)

Metal-organic coordination interactions are prime candidates for the formation of self-assembled, nanometer-scale periodic networks with room-temperature structural stability. We present X-ray photoelectron spectroscopy measurements of such networks at the Cu(100) surface which provide clear evidence for genuine metal-organic coordination. This is evident as binding energy shifts in the O 1s and Fe 3p photoelectron peaks, corresponding to O and Fe atoms involved in the coordination. Our results provide the first clear evidence for charge-transfer coordination in metal-organic networks at surfaces and demonstrate a well-defined oxidation state for the coordinated Fe ions.

n-alkanes on MgO(100). I. Coverage-dependent desorption kinetics of n-butane

High-quality temperature-programmed desorption (TPD) measurements of n-butane from MgO(100) have been made for a large number of initial butane coverages (0-3.70 ML, ML-monolayers) and a wide range of heating ramp rates (0.3-10 K/s). We present a TPD analysis technique which allows the coverage-dependent desorption energy to be accurately determined by mathematical inversion of a TPD spectrum, assuming only that the preexponential factor (prefactor) is coverage independent. A variational method is used to determine the prefactor that minimizes the difference between a set of simulated TPD spectra and corresponding experimental data. The best fit for butane desorption from MgO is obtained with a prefactor of 10(15.7+/-1.6) s(-1). The desorption energy is 34.9+/-3.4 kJ/mol at 0.5-ML coverage, and varies with coverage approximately as Ed(theta)=34.5+0.566theta+8.37 exp(-theta/0.101). Simulations based on these results can accurately reproduce TPD experiments for submonolayer initial coverages over a wide range of heating ramp rates (0.3-10 K/s). Advantages and limitations of this method are discussed.

Ordering and Stabilization of Metal-Organic Coordination Chains by Hierarchical Assembly through Hydrogen Bonding at a Surface

Keywords: copper ; scanning probe microscopy ; self-assembly ; supramolecular chemistry ; surface chemistry ; Cu(100) ; Networks ; Chemistry ; Template ; Polymers ; Acid ; Architectures ; Confinement ; Interface ; Molecules Reference EPFL-ARTICLE-160497doi:10.1002/anie.200803124View record in Web of Science Record created on 2010-11-30, modified on 2017-05-12

Assembling Isostructural Metal‐Organic Coordination Architectures on Cu(100), Ag(100) and Ag(111) Substrates

Keywords: bipyrimidine ligands ; nanostructures ; scanning probe microscopy ; self-assembly ; supramolecular chemistry ; Scanning-Tunneling-Microscopy ; Oriented Pyrolytic-Graphite ; Weak Hydrogen-Bonds ; Terephthalic Acid ; Surface ; Networks ; Coadsorption ; Organization ; Monolayers ; Interface Reference EPFL-ARTICLE-160376doi:10.1002/cphc.200800575View record in Web of Science Record created on 2010-11-30, modified on 2017-05-12