A facile, rapid, and scalable electrophoretic deposition approach is developed for the fabrication of large-area chemically derived graphene films on conductive substrates based on the electrophoretic deposition of graphene oxide and reduced graphene oxide components. Two distinctive approaches for fabricating conformal graphene films are developed. In the first approach, graphene oxide sheets are electrophoretically deposited from an aqueous solution after the oxidation of graphite to graphite oxide and the subsequent exfoliation of graphite oxide to graphene oxide. Next, the graphene oxide films are reduced via dip-coating in an aqueous solution of hydrazine. In the second approach, graphene oxide is reduced to graphene nanosheets in a strongly alkaline solution and the reduced graphene sheets are directly electrophoretically deposited onto conductive substrates. The film thickness can be modified by the deposition time and the obtained films span several square millimeters in area. Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is used to study the surface chemistry, electronic band structure, and degree of alignment of the electrophoretically deposited films. Polarized NEXAFS measurements verify the presence of epoxide surface functionalities on the graphene basal planes and indicate significant recovery of extended π-bonded networks upon defunctionalization by hydrazine treatment. These measurements further indicate significantly improved alignment of the graphene sheet components of the films parallel to the substrate surface when defunctionalization is performed prior to electrophoretic deposition.

The first-order metal-insulator phase transition in VO(2) is characterized by an ultrafast several-orders-of-magnitude change in electrical conductivity and optical transmittance, which makes this material an attractive candidate for the fabrication of optical limiting elements, thermochromic coatings, and Mott field-effect transistors. Here, we demonstrate that the phase-transition temperature and hysteresis can be tuned by scaling VO(2) to nanoscale dimensions. A simple hydrothermal protocol yields anisotropic free-standing single-crystalline VO(2) nanostructures with a phase-transition temperature depressed to as low as 32 degrees C from 67 degrees C in the bulk. The observations here point to the importance of carefully controlling the stoichiometry and dimensions of VO(2) nanostructures to tune the phase transition in this system.

The peculiarities in the electronic structure of the seemingly simple binary vanadium oxide VO2, as manifested in a pronounced metal−insulator phase transition in proximity to room temperature, have made it the subject of extensive theoretical and experimental investigations over the last several decades. We review some recent advances in theoretical treatments of strongly correlated systems along with ultrafast measurements of VO2 samples that provide unprecedented mechanistic insight into the nature of the phase transition. Scaling VO2 to nanoscale dimensions has recently been possible and has allowed well-defined VO2 nanostructures to serve as model systems for measurements of intrinsic properties without obscuration from grain boundary connectivities and domain dynamics. Geometric confinement, substrate interactions, and varying defect densities of VO2 nanostructures give rise to an electronic and structural phase diagram that is substantially altered from the bulk. We postulate that design principles deduced from fundamental understanding of phase transitions in nanostructures will allow the predictive and rational design of systems with tunable charge and spin ordering.

The influence of finite size in altering the phase stabilities of strongly correlated materials gives rise to the interesting prospect of achieving additional tunability of solid-solid phase transitions such as those involved in metal-insulator switching, ferroelectricity, and superconductivity. We note here some distinctive finite size effects on the relative phase stabilities of insulating (monoclinic) and metallic (tetragonal) phases of solid-solution W x V 1Àx O 2 . Ensemble differential scanning calorimetry and individual nanobelt electrical transport measurements suggest a pronounced hysteresis between metal / insulator and insulator / metal phase transformations. Both transitions are depressed to lower critical temperatures upon the incorporation of substitutional tungsten dopants but the impact on the former transition seems far more prominent. In general, the depression in the critical temperatures upon tungsten doping far exceeds corresponding values for bulk W x V 1Àx O 2 of the same composition. Notably, the depression in phase transition temperature saturates at a relatively low dopant concentration in the nanobelts, thought to be associated with the specific sites occupied by the tungsten substitutional dopants in these structures. The marked deviations from bulk behavior are rationalized in terms of a percolative model of the phase transition taking into account the nucleation of locally tetragonal domains and enhanced carrier delocalization that accompany W 6+ doping in the W x V 1Àx O 2 nanobelts.