Borophenes made easy.

To date, the scalable synthesis of elemental two-dimensional materials beyond graphene still remains elusive. Here, we introduce a versatile chemical vapor deposition (CVD) method to grow borophenes, as well as borophene heterostructures, by selectively using diborane originating from traceable byproducts of borazine. Specifically, metallic borophene polymorphs were successfully synthesized on Ir(111) and Cu(111) single-crystal substrates and conjointly with insulating hexagonal boron nitride (hBN) to form atomically precise lateral borophene-hBN interfaces or vertical van der Waals heterostructures. Thereby, borophene is protected from immediate oxidation by a single hBN overlayer. The ability to synthesize high-quality borophenes with large single-crystalline domains in the micrometer scale by a straight-forward CVD approach opens up opportunities for the study of their fundamental properties and for device incorporation.

On-Surface Synthesis of BN-Substituted Heteroaromatic Networks.

We report on the bottom-up fabrication of BN-substituted heteroaromatic networks achieved by surface-assisted polymerization and subsequent cyclodehydrogenation of specifically designed BN-substituted precursor monomers based on a borazine core structural element. To get insight into the cyclodehydrogenation pathway and the influence of molecular flexibility on network quality, two closely related precursor monomers with different degrees of internal cyclodehydrogenation have been employed. Scanning tunneling microscopy shows that, for both monomers, surface-assisted cyclodehydrogenation allows for complete monomer cyclization and the formation of covalently interlinked BN-substituted polyaromatic hydrocarbon networks on the Ag(111) surface. In agreement with experimental observations, density functional theory calculations reveal a significantly lower energy barrier for the cyclodehydrogenation of the conformationally more rigid precursor monomer, which is also reflected in a higher degree of long-range order of the obtained heteroaromatic network. Our proof-of-concept study will allow for the fabrication of atomically precise substitution patterns within BNC heterostructures.

Tuning the Magnetic Properties of Carbon by Nitrogen Doping of Its Graphene Domains.

Here we present the formation of predominantly sp(2)-coordinate carbon with magnetic- and heteroatom-induced structural defects in a graphene lattice by a stoichiometric dehalogenation of perchlorinated (hetero)aromatic precursors [hexachlorobenzene, C6Cl6 (HCB), and pentachloropyridine, NC5Cl5 (PCP)] with transition metals such as copper in a combustion synthesis. This route allows the build-up of a carbon lattice by a chemistry free of hydrogen and oxygen compared to other pyrolytic approaches and yields either nitrogen-doped or -undoped graphene domains depending on the precursor. The resulting carbon was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, photoelectron spectroscopy (XPS), and SQUID magnetometry to gain information on its morphological, chemical, and electronic structure and on the location of the nitrogen atoms within the carbon lattice. A significant lowering of the magnetization was observed for the nitrogen-doped carbon obtained by this method, which exhibits less ordered graphene domains in the range of approximately 10-30 nm as per TEM analysis compared to the nondoped carbon resulting from the reaction of HCB with larger graphene domains as per TEM and the presence of a 2D mode in the Raman spectra. The decrease of the magnetization by nitrogen doping within the sp(2)-coordinate carbon lattice can be attributed to an increase in pyrrole-type defects along with a reduction in radical defects originating from five-membered carbon ring structures as well as changes in the π-electron density of edge states.

Chemical vapor deposition of high quality graphene films from carbon dioxide atmospheres.

The realization of graphene-based, next-generation electronic applications essentially depends on a reproducible, large-scale production of graphene films via chemical vapor deposition (CVD). We demonstrate how key challenges such as uniformity and homogeneity of the copper metal substrate as well as the growth chemistry can be improved by the use of carbon dioxide and carbon dioxide enriched gas atmospheres. Our approach enables graphene film production protocols free of elemental hydrogen and provides graphene layers of superior quality compared to samples produced by conventional hydrogen/methane based CVD processes. The substrates and resulting graphene films were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and Raman microscopy, sheet resistance and transport measurements. The superior quality of the as-grown graphene films on copper is indicated by Raman maps revealing average G band widths as low as 18 ± 8 cm(-1) at 514.5 nm excitation. In addition, high charge carrier mobilities of up to 1975 cm(2)/(V s) were observed for electrons in transferred films obtained from a carbon dioxide based growth protocol. The enhanced graphene film quality can be explained by the mild oxidation properties of carbon dioxide, which at high temperatures enables an uniform conditioning of the substrates by an efficient removal of pre-existing and emerging carbon impurities and a continuous suppression and in situ etching of carbon of lesser quality being co-deposited during the CVD growth.

Magnetoresistance and charge transport in graphene governed by nitrogen dopants.

We identify the influence of nitrogen-doping on charge- and magnetotransport of single layer graphene by comparing doped and undoped samples. Both sample types are grown by chemical vapor deposition (CVD) and transferred in an identical process onto Si/SiO2 wafers. We characterize the samples by Raman spectroscopy as well as by variable temperature magnetotransport measurements. Over the entire temperature range, the charge transport properties of all undoped samples are in line with literature values. The nitrogen doping instead leads to a 6-fold increase in the charge carrier concentration up to 4 × 10(13) cm(-2) at room temperature, indicating highly effective doping. Additionally it results in the opening of a charge transport gap as revealed by the temperature dependence of the resistance. The magnetotransport exhibits a conspicuous sign change from positive Lorentz magnetoresistance (MR) in undoped to large negative MR that we can attribute to the doping induced disorder. At low magnetic fields, we use quantum transport signals to quantify the transport properties. Analyses based on weak localization models allow us to determine an orders of magnitude decrease in the phase coherence and scattering times for doped samples, since the dopants act as effective scattering centers.

Dehalogenation and coupling of a polycyclic hydrocarbon on an atomically thin insulator.

Catalytic activity is of pivotal relevance in enabling efficient and selective synthesis processes. Recently, covalent coupling reactions catalyzed by solid metal surfaces opened the rapidly evolving field of on-surface chemical synthesis. Tailored molecular precursors in conjunction with the catalytic activity of the metal substrate allow the synthesis of novel, technologically highly relevant materials such as atomically precise graphene nanoribbons. However, the reaction path on the metal substrate remains unclear in most cases, and the intriguing question is how a specific atomic configuration between reactant and catalyst controls the reaction processes. In this study, we cover the metal substrate with a monolayer of hexagonal boron nitride (h-BN), reducing the reactivity of the metal, and gain unique access to atomistic details during the activation of a polyphenylene precursor by sequential dehalogenation and the subsequent coupling to extended oligomers. We use scanning tunneling microscopy and density functional theory to reveal a reaction site anisotropy, induced by the registry mismatch between the precursor and the nanostructured h-BN monolayer.

Chemical vapor deposition of N-doped graphene and carbon films: the role of precursors and gas phase.

Thermally induced chemical vapor deposition (CVD) was used to study the formation of nitrogen-doped graphene and carbon films on copper from aliphatic nitrogen-containing precursors consisting of C1- and C2-units and (hetero)aromatic nitrogen-containing ring systems. The structure and quality of the resulting films were correlated to the influence of the functional groups of the precursor molecules and gas phase composition. They were analyzed with SEM, TEM, EDX, XPS, and Raman spectroscopy. The presence of (N-doped) graphene was confirmed by the 2D mode of the Raman spectra. The isolated graphene films obtained from nitrogen-containing precursors reveal a high conductivity and transparency compared to standard graphene CVD samples. Precursors with amine functional groups (e.g., methylamine) can lead to a direct formation of graphene even without additional hydrogen present in the gas phase. This is not observed for, e.g., methane under comparable CVD conditions. Therefore, the intermediate gas phase species (e.g., amine radicals) can significantly enhance the graphene film growth kinetics. Kinetic and thermodynamic effects can be invoked to discuss the decay of the precursors.

Control of molecular organization and energy level alignment by an electronically nanopatterned boron nitride template.

Suitable templates to steer the formation of nanostructure arrays on surfaces are indispensable in nanoscience. Recently, atomically thin sp(2)-bonded layers such as graphene or boron nitride (BN) grown on metal supports have attracted considerable interest due to their potential geometric corrugation guiding the positioning of atoms, metallic clusters or molecules. Here, we demonstrate three specific functions of a geometrically smooth, but electronically corrugated, sp(2)/metal interface, namely, BN/Cu(111), qualifying it as a unique nanoscale template. As functional adsorbates we employed free-base porphine (2H-P), a prototype tetrapyrrole compound, and tetracyanoquinodimethane (TCNQ), a well-known electron acceptor. (i) The electronic moirons of the BN/Cu(111) interface trap both 2H-P and TCNQ, steering self-organized growth of arrays with extended molecular assemblies. (ii) We report an effective decoupling of the trapped molecules from the underlying metal support by the BN, which allows for a direct visualization of frontier orbitals by scanning tunneling microscopy (STM). (iii) The lateral molecular positioning in the superstructured surface determines the energetic level alignment; i.e., the energy of the frontier orbitals, and the electronic gap are tunable.

High-performance electrocatalysts for oxygen reduction derived from cobalt porphyrin-based conjugated mesoporous polymers.

A cobalt-nitrogen-doped porous carbon that exhibits a ribbon-shape morphology, high surface area, mesoporous structure, and high nitrogen and cobalt content is fabricated for high-performance self-supported oxygen reduction electrocatalytsts through template-free pyrolysis of cobalt porphyrin-based conjugated mesoporous polymer frameworks.

Boron nitride on Cu(111): an electronically corrugated monolayer.

Ultrathin films of boron nitride (BN) have recently attracted considerable interest given their successful incorporation in graphene nanodevices and their use as spacer layers to electronically decouple and order functional adsorbates. Here, we introduce a BN monolayer grown by chemical vapor deposition of borazine on a single crystal Cu support, representing a model system for an electronically patterned but topographically smooth substrate. Scanning tunneling microscopy and spectroscopy experiments evidence a weak bonding of the single BN sheet to Cu, preserving the insulating character of bulk hexagonal boron nitride, combined with a periodic lateral variation of the local work function and the surface potential. Complementary density functional theory calculations reveal a varying registry of the BN relative to the Cu lattice as origin of this electronic Moiré-like superstructure.

Probing the selectivity of a nanostructured surface by xenon adsorption.

Surface-supported molecular self-assembly with the goal to produce highly ordered, functional supramolecular nanostructures are often realized using nanopatterned surfaces, which exhibit long range - ideally periodic - modulations of the molecule adsorption properties. To elucidate the physical origins of the site-specific adsorption properties of such a nanopatterned substrate, we investigated the temperature-dependent microscopic structure and the dynamics of adsorbed Xe at different temperatures on single-sheet h-BN on a Rh(111) nanomesh. In combination with molecular dynamics simulations we show that the site-specific adsorption arises from two different interactions of similar magnitude with respect to their lateral variations. The first can be attributed to a van der Waals type interaction, whereas the second originates from lateral variation of the electrostatic surface potential and is of polarization type. Both types lead to an adsorption energy minimum at the rim of the nanomesh pore and are therefore responsible for stabilizing dynamic and static Xe rings in these pores. The insight into this interplay of interactions should pave the way to gain a more general knowledge on such site-specific adsorption processes.

How does graphene grow? Easy access to well-ordered graphene films.

The selective formation of large-scale graphene layers on a Rh-YSZ-Si(111) multilayer substrate by a surface-induced chemical growth mechanism is investigated using low-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray photoelectron diffraction, and scanning tunneling microscopy. It is shown that well-ordered graphene layers can be grown using simple and controllable procedures. In addition, temperature-dependent experiments provide insight into the details of the growth mechanisms. A comparison of different precursors shows that a mobile dicarbon species (e.g., C(2)H(2) or C(2)) acts as a common intermediate for graphene formation. These new approaches offer scalable methods for the large-scale production of high-quality graphene layers on silicon-based multilayer substrates.