Exfoliation of Graphene onto Si(111)-7 × 7 under Ultrahigh Vacuum Provides Some Protection against Exposure to Air.

The investigation of graphene as a protective coating for different materials has been an area of active research for well over a decade. However, graphene's ability to protect clean, reconstructed silicon from ambient gases has remained uninvestigated. Here, we describe the use of a clean ultrahigh vacuum transfer method to deposit graphene onto the Si(111)-7 × 7 reconstruction.

Innovations in nanosynthesis: emerging techniques for precision, scalability, and spatial control in reactions of organic molecules on solid surfaces.

The surface science-based approach to synthesising new organic materials on surfaces has gained considerable attention in recent years, owing to its success in facilitating the formation of novel 0D, 1D and 2D architectures. The primary mechanism used to date has been the catalytic transformation of small organic molecules through substrate-enabled reactions. In this Topical Review, we provide an overview of alternate approaches to controlling molecular reactions on surfaces.

High quality epitaxial graphene on 4H-SiC by face-to-face growth in ultra-high vacuum.

Epitaxial graphene on SiC is the most promising substrate for the next generation 2D electronics, due to the possibility to fabricate 2D heterostructures directly on it, opening the door to the use of all technological processes developed for silicon electronics. To obtain a suitable material for large scale applications, it is essential to achieve perfect control of size, quality, growth rate and thickness. Here we show that this control on epitaxial graphene can be achieved by exploiting the face-to-face annealing of SiC in ultra-high vacuum.

Degradation of Melt Electrowritten PCL Scaffolds Following Melt Processing and Plasma Surface Treatment.

Melt electrowriting (MEW) has been widely used to process polycaprolactone (PCL) into highly ordered microfiber scaffolds with controllable architecture and geometry. However, the integrity of PCL during specific processes involved in routine MEW scaffold development has not yet been thoroughly investigated. This study investigates the impact of MEW processing on PCL following exposure to high temperatures required for melt extrusion as well as atmospheric plasma, a widely used surface treatment for improving MEW scaffold hydrophilicity.

Identification of Topotactic Surface-Confined Ullmann-Polymerization.

On-surface Ullmann coupling is an established method for the synthesis of 1D and 2D organic structures. A key limitation to obtaining ordered polymers is the uncertainty in the final structure for coupling via random diffusion of reactants over the substrate, which leads to polymorphism and defects. Here, a topotactic polymerization on Cu(110) in a series of differently-halogenated para-phenylenes is identified, where the self-assembled organometallic (OM) reactants of diiodobenzene couple directly into a single, deterministic product, whereas the other precursors follow a diffusion driven reaction.

Engineering of SnO-Graphene Oxide Nanoheterojunctions for Selective Room-Temperature Chemical Sensing and Optoelectronic Devices.

The development of high-performing sensing materials, able to detect ppb-trace concentrations of volatile organic compounds (VOCs) at low temperatures, is required for the development of next-generation miniaturized wireless sensors. Here, we present the engineering of selective room-temperature (RT) chemical sensors, comprising highly porous tin dioxide (SnO)-graphene oxide (GO) nanoheterojunction layouts. The optoelectronic and chemical properties of these highly porous (>90%) p-n heterojunctions were systematically investigated in terms of composition and morphologies.

One-Step Synthesis of Porous Transparent Conductive Oxides by Hierarchical Self-Assembly of Aluminum-Doped ZnO Nanoparticles.

Transparent conductive oxides (TCOs) are highly desirable for numerous applications ranging from photovoltaics to light-emitting diodes and photoelectrochemical devices. Despite progress, it remains challenging to fabricate porous TCOs (pTCOs) that may provide, for instance, a hierarchical nanostructured morphology for the separation of photoexcited hole/electron couples. Here, we present a facile process for the fabrication of porous architectures of aluminum-doped zinc oxide (AZO), a low-cost and earth-abundant transparent conductive oxide.

Room-temperature photodetectors and VOC sensors based on graphene oxide-ZnO nano-heterojunctions.

The rapid development of smart wearable electronics is driving the engineering of novel miniaturized sensing materials that can rapidly respond to very small changes in the concentration of biomarkers at room temperature. Carbon-based nanomaterials offer numerous attractive properties such as low resistivity, good mechanical robustness and integration potential, but lack a strong detection and transduction mechanism for the measurement of chemical molecules or photons. Here, we present a three-dimensional nanostructured architecture comprising optimally integrated graphene oxide (GO)-ZnO heterojunctions for the room temperature sensing of volatile biomarkers.

Cleaning up after the Party: Removing the Byproducts of On-Surface Ullmann Coupling.

Ullmann coupling is one of the most frequently employed methodologies for producing π-conjugated surface-confined polymers. One unfortunate side product of the reaction is the creation of metal halide islands formed from liberated halogen atoms. Following the coupling reaction, these halide islands can account for a large proportion of the substrate surface area and thus inhibit domain growth and effectively poison the catalyst.

Adsorption, Deprotonation, and Decarboxylation of Isophthalic Acid on Cu(111).

The surface-assisted reaction of rationally designed organic precursors is an emerging approach toward fabricating atomically precise nanostructures. Recently, on-surface decarboxylation has attracted attention due to its volatile by-products, which tend to leave the surface during the reaction means only the desired products are retained on the surface. However, in addition to acting as the reactive site, the carboxylic acid groups play a vital role in the adsorption configuration of small-molecule molecular precursors and therefore in the reaction pathways.

An unexpected organometallic intermediate in surface-confined Ullmann coupling.

Ullmann coupling or, more generally, dehalogenative aryl-aryl coupling, is one of the most widely exploited chemical reactions to obtain one- and two-dimensional polymers on metal surfaces. It is generally described as a two-step reaction: (i) dehalogenation, resulting in the formation of a stable intermediate organometallic phase and subsequent (ii) C-C coupling. The topology of the resulting polymer depends on the number and positions of the halogen atoms in the haloaromatic precursor, although its orientation and order are determined by the structure of the intermediate phase.

Electron effective attenuation length in epitaxial graphene on SiC.

The inelastic mean free path (IMFP) for carbon-based materials is notoriously challenging to model, and moving from bulk materials to 2D materials may exacerbate this problem, making the accurate measurements of IMFP in 2D carbon materials critical. The overlayer-film method is a common experimental method to estimate IMFP by measuring electron effective attenuation length (EAL). This estimation relies on an assumption that elastic scattering effects are negligible.

On-surface synthesis of polyethylenedioxythiophene.

On-surface synthesis of conjugated polymers is made challenging by the need to promote the desired reaction while preventing or minimizing unwanted ancillary reactions that compromise the product integrity. We perform a comprehensive study of the reactions of 2,5-dichloro-3,4-ethylenedioxythiophene on coinage metal surfaces, and demonstrate that only on Ag(111) can we obtain a planar polymer product, polyethylenedioxythiophene (PEDOT).

Quasi free-standing epitaxial graphene fabrication on 3C-SiC/Si(111).

Growing graphene on SiC thin films on Si is a cheaper alternative to the growth on bulk SiC, and for this reason it has been recently intensively investigated. Here we study the effect of hydrogen intercalation on epitaxial graphene obtained by high temperature annealing on 3C-SiC/Si(111) in ultra-high vacuum. By using a combination of core-level photoelectron spectroscopy, low energy electron diffraction, and near-edge x-ray absorption fine structure (NEXAFS) we find that hydrogen saturates the Si atoms at the topmost layer of the substrate, leading to free-standing graphene on 3C-SiC/Si(111).

A 2D Substitutional Solid Solution through Hydrogen Bonding of Molecular Building Blocks.

Two-dimensional (2D) molecular self-assembly allows for the formation of well-defined supramolecular layers with tailored geometrical, compositional, and chemical properties. To date, random intermixing and entropic effects in these systems have largely been associated with crystalline disorder and glassy phases. Here we describe a 2D crystalline self-assembled molecular system that exhibits random incorporation of substitutional molecules.

The role of halogens in on-surface Ullmann polymerization.

Ullmann coupling is the most common approach to form surface-confined one- and two-dimensional conjugated structures from haloaryl derivatives. The dimensions of the formed nanostructures can be controlled by the number and location of halogens within the molecular precursors. Our study illustrates that the type of halogen plays an essential role in the design, orientation, and extent of the surface-confined organometallic and polymeric nanostructures.

Epitaxial graphene growth on FIB patterned 3C-SiC nanostructures on Si (111): reducing milling damage.

Epitaxial growth of graphene on SiC is a scalable procedure that does not require any further transfer step, making this an ideal platform for graphene nanostructure fabrication. Focused ion beam (FIB) is a very promising tool for exploring the reduction of the lateral dimension of graphene on SiC to the nanometre scale. However, exposure of graphene to the Ga beam causes significant surface damage through amorphisation and contamination, preventing epitaxial graphene growth.

High quality epitaxial graphene by hydrogen-etching of 3C-SiC(111) thin-film on Si(111).

Etching with atomic hydrogen, as a preparation step before the high-temperature growth process of graphene onto a thin 3C-SiC film grown on Si(111), greatly improves the structural quality of topmost graphene layers. Pit formation and island coalescence, which are typical of graphene growth by SiC graphitization, are quenched and accompanied by widening of the graphene domain sizes to hundreds of nanometers, and by a significant reduction in surface roughness down to a single substrate bilayer. The surface reconstructions expected for graphene and the underlying layer are shown with atomic resolution by scanning tunnelling microscopy.

Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization.

Surface-confined polymerization via Ullmann coupling is a promising route to create one- and two-dimensional covalent π-conjugated structures, including the bottom-up growth of graphene nanoribbons. Understanding the mechanism of the Ullmann reaction is necessary to provide a platform for rationally controlling the formation of these materials. We use fast X-ray photoelectron spectroscopy (XPS) in kinetic measurements of epitaxial surface polymerization of 1,4-dibromobenzene on Cu(110) and devise a kinetic model based on mean field rate equations, involving a transient state.

Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires.

On-surface covalent self-assembly of organic molecules is a very promising bottom-up approach for producing atomically controlled nanostructures. Due to their highly tuneable properties, these structures may be used as building blocks in electronic carbon-based molecular devices. Following this idea, here we report on the electronic structure of an ordered array of poly(para-phenylene) nanowires produced by surface-catalysed dehalogenative reaction.

Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces.

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV).

Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver.

We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C.

Insight into organometallic intermediate and its evolution to covalent bonding in surface-confined ullmann polymerization.

We provide insight into surface-catalyzed dehalogenative polymerization, analyzing the organometallic intermediate and its evolution into planar polymeric structures. A combined study using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and first-principles calculations unveils the structural conformation of substrate-bound phenylene intermediates generated from 1,4-dibromobenzene precursors on Cu(110), showing the stabilizing role of the halogen. The appearance of covalently bonded conjugated structures is followed in real time by fast-XPS measurements (with an acquisition time of 2 s per spectrum and heating rate of 2 K/s), showing that the detaching of phenylene units from the copper substrate and subsequent polymerization occur upon annealing above 460 ± 10 K.

Self-assembly of a halogenated molecule on oxide-passivated Cu(110).

The supramolecular self-assembly of brominated molecules was investigated and compared on Cu(110) and Cu(110)-O(2×1) surfaces under ultrahigh vacuum. By using scanning tunnelling microscopy, we show that brominated molecules form a disordered structure on Cu(110), whereas a well-ordered supramolecular network is observed on the Cu(110)-O(2×1) surface. The different adsorption behaviors of these two surfaces are described in terms of weakened molecule-substrate interactions on Cu(110)-O(2×1) as opposed to bare Cu(110).