Effect of friction on oxidative graphite intercalation and high-quality graphene formation.

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In2O3(111): Nanomanipulation and Theory.

Changes in chemical and physical properties resulting from water adsorption play an important role in the characterization and performance of device-relevant materials. Studies of model oxides with well-characterized surfaces can provide detailed information that is vital for a general understanding of water-oxide interactions. In this work, we study single crystals of indium oxide, the prototypical transparent contact material that is heavily used in a wide range of applications and most prominently in optoelectronic technologies. Water adsorbs dissociatively already at temperatures as low as 100 K, as confirmed by scanning tunneling microscopy (STM), photoelectron spectroscopy, and density functional theory. This dissociation takes place on lattice sites of the defect-free surface. While the In2O3(111)-(1 × 1) surface offers four types of surface oxygen atoms (12 atoms per unit cell in total), water dissociation happens exclusively at one of them together with a neighboring pair of 5-fold coordinated In atoms. These O-In groups are symmetrically arranged around the 6-fold coordinated In atoms at the surface. At room temperature, the In2O3(111) surface thus saturates at three dissociated water molecules per unit cell, leading to a well-ordered hydroxylated surface with (1 × 1) symmetry, where the three water OWH groups plus the surface OSH groups are imaged together as one bright triangle in STM. Manipulations with the STM tip by means of voltage pulses preferentially remove the H atom of one surface OSH group per triangle. The change in contrast due to strong local band bending provides insights into the internal structure of these bright triangles. The experimental results are further confirmed by quantitative simulations of the STM image corrugation.

Well-Ordered In Adatoms at the In_{2}O_{3}(111) Surface Created by Fe Deposition.

Metal deposition on oxide surfaces usually results in adatoms, clusters, or islands of the deposited material, where defects in the surface often act as nucleation centers. Here an alternate configuration is reported. After the vapor deposition of Fe on the In_{2}O_{3}(111) surface at room temperature, ordered adatoms are observed with scanning tunneling microscopy. These are identical to the In adatoms that form when the sample is reduced by heating in ultrahigh vacuum. Density functional theory calculations confirm that Fe interchanges with In in the topmost layer, pushing the excess In atoms to the surface where they arrange as a well-ordered adatom array.

Interface chemistry and molecular bonding of functional ethoxysilane-based self-assembled monolayers on magnesium surfaces.

The modification of magnesium implants with functional organic molecules is important for increasing the biological acceptance and for reducing the corrosion rate of the implant. In this work, we evaluated by a combined experimental and theoretical approach the adsorption strength and geometry of a functional self-assembled monolayer (SAM) of hydrolyzed (3-aminopropyl)triethoxysilane (APTES) molecules on a model magnesium implant surface. In time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS), only a minor amount of reverse attachment was observed. Substrate-O-Si signals could be detected, as well as other characteristic APTES fragments. The stability of the SAM upon heating in UHV was investigated additionally. Density-functional theory (DFT) calculations were used to explore the preferred binding mode and the most favorable binding configuration of the hydrolyzed APTES molecules on the hydroxylated magnesium substrate. Attachment of the molecules via hydrogen bonding or covalent bond formation via single or multiple condensation reactions were considered. The impact of the experimental conditions and the water concentration in the solvent on the thermodynamic stability of possible APTES binding modes is analyzed as a function of the water chemical potential of the environment. Finally, the influence of van der Waals contributions to the adsorption energy will be discussed.

Electron Beam-Induced Writing of Nanoscale Iron Wires on a Functional Metal Oxide.

Electron beam-induced surface activation (EBISA) has been used to grow wires of iron on rutile TiO2(110)-(1 × 1) in ultrahigh vacuum. The wires have a width down to ∼20 nm and hence have potential utility as interconnects on this dielectric substrate. Wire formation was achieved using an electron beam from a scanning electron microscope to activate the surface, which was subsequently exposed to Fe(CO)5. On the basis of scanning tunneling microscopy and Auger electron spectroscopy measurements, the activation mechanism involves electron beam-induced surface reduction and restructuring.