Nonequilibrium carrier dynamics in single exfoliated graphene layers on muscovite substrates are studied by ultrafast optical pump-probe spectroscopy and compared with microscopic theory. The very high 10-fs-time resolution allows for mapping the ultrafast carrier equilibration into a quasi-Fermi distribution and the subsequent slower relaxation stages. Coulomb-mediated carrier-carrier and carrier-optical phonon scattering are essential for forming hot separate Fermi distributions of electrons and holes which cool by intraband optical phonon emission. Carrier cooling and recombination are influenced by hot phonon effects.

Graphitic carbon nitride has been predicted to be structurally analogous to carbon-only graphite, yet with an inherent bandgap. We have grown, for the first time, macroscopically large crystalline thin films of triazine-based, graphitic carbon nitride (TGCN) using an ionothermal, interfacial reaction starting with the abundant monomer dicyandiamide. The films consist of stacked, two-dimensional (2D) crystals between a few and several hundreds of atomic layers in thickness. Scanning force and transmission electron microscopy show long-range, in-plane order, while optical spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations corroborate a direct bandgap between 1.6 and 2.0 eV. Thus TGCN is of interest for electronic devices, such as field-effect transistors and light-emitting diodes.

Control of intermolecular interactions is crucial to the exploitation of molecular semiconductors for both organic electronics and the viable manipulation and incorporation of single molecules into nano-engineered devices. Here we explore the properties of a class of materials that are engineered at a supramolecular level by threading a conjugated macromolecule, such as poly(para-phenylene), poly(4,4'-diphenylene vinylene) or polyfluorene through alpha- or beta-cyclodextrin rings, so as to reduce intermolecular interactions and solid-state packing effects that red-shift and partially quench the luminescence. Our approach preserves the fundamental semiconducting properties of the conjugated wires, and is effective at both increasing the photoluminescence efficiency and blue-shifting the emission of the conjugated cores, in the solid state, while still allowing charge-transport. We used the polymers to prepare single-layer light-emitting diodes with Ca and Al cathodes, and observed blue and green emission. The reduced tendency for polymer chains to aggregate allows solution-processing of individual polyrotaxane wires onto substrates, as revealed by scanning force microscopy.

The hydration of graphene oxide (GO) membranes is the key to understand their remarkable selectivity in permeation of water molecules and humidity-dependent gas separation. We investigated the hydration of single GO layers as a function of humidity using scanning force microscopy, and we determined the single interlayer distance from the step height of a single GO layer on top of one or two GO layers. This interlayer distance grows gradually by approximately 1 Å upon a relative humidity (RH) increase in the range of 2 to ∼80%, and the immersion into liquid water increases the interlayer distance further by another 3 Å. The gradual expansion of the single interlayer distance is in good agreement with the averaged distance measured by X-ray diffraction on multilayered graphite oxides, which is commonly explained with an interstratification model. However, our experimental design excludes effects connected to interstratification. Instead we determine directly if insertion of water into GO occurs strictly by monolayers or the thickness of GO layers changes gradually. We find that hydration with up to 80% RH is a continuous process of incorporation of water molecules into single GO layers, while liquid water inserts as monolayers. The similarity of hydration for our bilayer and previously reported multilayered materials implies GO few and even bilayers to be suitable for selective water transport.

The behavior of water and other molecular liquids confined to the nanoscale is of fundamental importance, e.g., in biology, material science, nanofluidics, and tribology. Direct microscopic imaging of wetting dynamics in subnanometer pores is however challenging. We will show in the following that a molecularly thin water film confined between mica and graphene is fluid. Ambient humidity allows to control the wetting and dewetting of the film. We follow these processes in space and time using scanning force microscopy imaging of the graphene conforming to the film. At sufficiently high humidity a continuous molecularly thin water film wets the interface between the graphene and mica. At lower humidities the film dewets with fractal depressions exhibiting dimensions around 1.7 and depths comparable to the size of a water molecule. The soft graphene cover offers a previously unexplored semihydrophilic slit pore of self-adjustable size, which enables high-resolution imaging of confined molecularly thin fluid films, and bears the potential for the fabrication of novel nanofluidic devices.