Free-standing nanomembranes with molecular or atomic thickness are currently explored for separation technologies, electronics, and sensing. Their engineering with well-defined structural and functional properties is a challenge for materials research. Here we present a broadly applicable scheme to create mechanically stable carbon nanomembranes (CNMs) with a thickness of ~0.5 to ~3 nm. Monolayers of polyaromatic molecules (oligophenyls, hexaphenylbenzene, and polycyclic aromatic hydrocarbons) were assembled and exposed to electrons that cross-link them into CNMs; subsequent pyrolysis converts the CNMs into graphene sheets. In this transformation the thickness, porosity, and surface functionality of the nanomembranes are determined by the monolayers, and structural and functional features are passed on from the molecules through their monolayers to the CNMs and finally on to the graphene. Our procedure is scalable to large areas and allows the engineering of ultrathin nanomembranes by controlling the composition and structure of precursor molecules and their monolayers.

Self-assembled monolayers of aromatic molecules on copper substrates can be converted into high-quality single-layer graphene using low-energy electron irradiation and subsequent annealing. This two-dimensional solid state transformation is characterized on the atomic scale and the physical and chemical properties of the formed graphene sheets are studied by complementary microscopic and spectroscopic techniques and by electrical transport measurements. As substrates, Cu(111) single crystals and the technologically relevant polycrystalline copper foils are successfully used.

High-quality graphene oxide (GO) with high crystallinity and electrical conductivity as well as in situ doped with nitrogen and sulfur is obtained via the electrochemical exfoliation of graphite. Furthermore, iron incorporated GO sheets show promising catalytic activity and stable methanol tolerance durability when used as electrocatalysts for the oxygen reduction reaction.

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.

Controlling the type and density of charge carriers in graphene is vital for a wide range of applications of this material in electronics and optoelectronics. To date, chemical doping and electrostatic gating have served as the two most established means to manipulate the carrier density in graphene. Although highly effective, these two approaches require sophisticated graphene growth or complex device fabrication processes to achieve both the desired nature and the doping densities with generally limited dynamic tunability and spatial control. Here, we report a convenient and tunable optical approach to tune the steady-state carrier density and Fermi energy in graphene by photochemically controlling the concentration of adsorbed molecular O 2 , a p-dopant in graphene, using femtosecond pulsed laser irradiation in the UV range. As an all-optical approach, it allows spatial control over doping levels. Combined terahertz (THz) spectroscopy and electrical device measurements reveal that the Fermi level in laser-illuminated graphene can be controllably and reversibly tuned between p-and n-type in a large range (over ∼600 meV from −420 to +180 meV) by readily tuning the peak intensity and the duration of the laser irradiation treatment. Furthermore, we demonstrate that our photochemical approach for doping of graphene allows one to optically write doping structure with spatial control. Given the ease, effectiveness, and simplicity of the method, this photochemical doping mechanism offers a simple, reversible approach to control the steady-state electronic and optical properties of graphene.

The direct growth of single-layer graphene patterns via electron irradiation of aromatic self-assembled monolayers and subsequent annealing is demonstrated. In this way, a reduction in the number of necessary manufacturing steps is achieved. The formed micro- and nanostructures can be arbitrarily shaped and eventually implemented in a manifold of applications.

Ultrathin carbon nanomembranes (CNM) comprising crosslinked biphenyl precursors have been tested as support films for energy-filtered transmission electron microscopy (EFTEM) of biological specimens. Due to their high transparency CNM are ideal substrates for electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) of stained and unstained biological samples. Virtually background-free elemental maps of tobacco mosaic virus (TMV) and ferritin have been obtained from samples supported by ∼1nm thin CNM. Furthermore, we have tested conductive carbon nanomembranes (cCNM) comprising nanocrystalline graphene, obtained by thermal treatment of CNM, as supports for cryoEM of ice-embedded biological samples. We imaged ice-embedded TMV on cCNM and compared the results with images of ice-embedded TMV on conventional carbon film (CC), thus analyzing the gain in contrast for TMV on cCNM in a quantitative manner. In addition we have developed a method for the preparation of vitrified specimens, suspended over the holes of a conventional holey carbon film, while backed by ultrathin cCNM.

Atomically thin free-standing nanomembranes belong to the emerging class of materials with a great promise for basic research of two-dimensional (2D) systems and applications in nanotechnology. However, their synthesis and characterization remain a frontier challenge in chemical and physical research. Here, we demonstrate that atmospheric pressure (Ar/H 2 ) annealing in the range from 500 to 1000 °C of ∼1 nm thick carbon nanomembranes (CNMs) made of cross-linked aromatic self-assembled monolayers results in their conversion into free-standing sheets of covalently bonded, in-plane oriented graphene nanocrystals. Upon this transformation the electrical characteristics of CNMs evolve from insulating to conducting, which is accompanied by a change of the room temperature sheet resistivity by more than 5 orders of magnitude. We analyze this atmospheric pressure, temperature-induced transformation of CNMs employing various complementary spectroscopic and microscopic techniques, such as X-ray photoelectron spectroscopy, Raman spectroscopy, electron energy loss spectroscopy, optical microscopy, helium ion microscopy, atomic force microscopy, and transmission electron microscopy. In particular we studied the chemical, structural, and electronic properties of CNMs. We provide a comparative analysis of these data with the properties of pristine graphene, graphene oxide, and reduced graphene oxide sheets, which reveals both similarities and differences between these 2D materials.