Formation of Two-Dimensional Micelles on Graphene: Multi-Scale Theoretical and Experimental Study.

Graphene and related two-dimensional (2D) materials possess outstanding electronic and mechanical properties, chemical stability, and high surface area. However, to realize graphene's potential for a range of applications in materials science and nanotechnology there is a need to understand and control the interaction of graphene with tailored high-performance surfactants designed to facilitate the preparation, manipulation, and functionalization of new graphene systems. Here we report a combined experimental and theoretical study of the surface structure and dynamics on graphene of pyrene-oligoethylene glycol (OEG) -based surfactants, which have previously been shown to disperse carbon nanotubes in water. Molecular self-assembly of the surfactants on graphitic surfaces is experimentally monitored and optimized using a graphene coated quartz crystal microbalance in ambient and vacuum environments. Real-space nanoscale resolution nanomechanical and topographical mapping of submonolayer surfactant coverage, using ultrasonic and atomic force microscopies both in ambient and ultrahigh vacuum, reveals complex, multilength-scale self-assembled structures. Molecular dynamics simulations show that at the nanoscale these structures, on atomically flat graphitic surfaces, are dependent upon the surfactant OEG chain length and are predicted to display a previously unseen class of 2D self-arranged "starfish" micelles (2DSMs). While three-dimensional micelles are well-known for their widespread uses ranging from microreactors to drug-delivery vehicles, these 2DSMs possess the highly desirable and tunable characteristics of high surface affinity coupled with unimpeded mobility, opening up strategies for processing and functionalizing 2D materials.

ZnO-based thin film transistors employing aluminum titanate gate dielectrics deposited by spray pyrolysis at ambient air.

The replacement of SiO2 gate dielectrics with metal oxides of higher dielectric constant has led to the investigation of a wide range of materials with superior properties compared with SiO2. Despite their attractive properties, these high-k dielectrics are usually manufactured using costly vacuum-based techniques. To overcome this bottleneck, research has focused on the development of alternative deposition methods based on solution-processable metal oxides. Here we report the application of spray pyrolysis for the deposition and investigation of Al2x-1·TixOy dielectrics as a function of the [Ti(4+)]/[Ti(4+)+2·Al(3+)] ratio and their implementation in thin film transistors (TFTs) employing spray-coated ZnO as the active semiconducting channels. The films are studied by UV-visible absorption spectroscopy, spectroscopic ellipsometry, impedance spectroscopy, atomic force microscopy, X-ray diffraction and field-effect measurements. Analyses reveal amorphous Al2x-1·TixOy dielectrics that exhibit a wide band gap (∼4.5 eV), low roughness (∼0.9 nm), high dielectric constant (k ∼ 13), Schottky pinning factor S of ∼0.44 and very low leakage currents (<5 nA/cm(2)). TFTs employing stoichiometric Al2O3·TiO2 gate dielectrics and ZnO semiconducting channels exhibit excellent electron transport characteristics with low operating voltages (∼10 V), negligible hysteresis, high on/off current modulation ratio of ∼10(6), subthreshold swing (SS) of ∼550 mV/dec and electron mobility of ∼10 cm(2) V(-1) s(-1).