Zinc oxide (ZnO) films were grown by radio frequency magnetron sputter deposition and the changes to its surface composition and workfunction induced by argon sputter cleaning and oxygen plasma treatments were characterized using x-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and density functional theory modelling. Compared with a workfunction of 3.74 eV for the as-deposited ZnO films, a workfunction of 3.95 eV was obtained after Ar sputter cleaning and 4.21 eV after exposure to oxygen plasma. The data indicate that oxygen plasma treatment leads to a more negative ZnO surface. The dipole induced by this charge redistribution reinforces the original surface dipole, which results in an increase in the surface dipole moment and an increase in workfunction. The reverse is true for hydrocarbon contamination of ZnO surfaces. Excellent qualitative agreement between the experimental results and computational modelling was obtained. The results suggest that specific surface functionalization may be a viable method of controlling the workfunction of ZnO for use as the transparent conducting oxide in optoelectronic applications such as solar cells and organic light-emitting diodes.

The diimine-dithiolato ambipolar complexes Pt(dbbpy)(tdt) and Pt(dmecb)(bdt) (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine; tdt(2-) = 3,4-toluenedithiolate; dmecb = 4,4'-dimethoxyester-2,2'-bipyridine; bdt(2-) = benzene-1,2-dithiolate) are prepared herein. Pt(dmecb)(bdt) exhibits photoconductivity that remains constant (photocurrent density of 1.6 mA/cm(2) from a 20 nm thin film) across the entire visible region of the solar spectrum in a Schottky diode device structure. Pt(dbbpy)(tdt) acts as donor when combined with the strong nitrofluorenone acceptors 2,7-dinitro-9-fluorenone (DNF), 2,4,7-trinitro-9-fluorenone (TRNF), or 2,4,5,7-tetranitro-9-fluorenone (TENF). Supramolecular charge transfer stacks form and exhibit various donor-acceptor stacking patterns. The crystalline solids are "black absorbers" that exhibit continuous absorptions spanning the entire visible region and significant ultraviolet and near-infrared wavelengths, the latter including long wavelengths that the donor or acceptor molecules alone do not absorb. Absorption spectra reveal the persistence of donor-acceptor interactions in solution, as characterized by low-energy donor/acceptor charge transfer (DACT) bands. Crystal structures show closely packed stacks with distances that underscore intermolecular DACT. (1)H NMR provides further evidence of DACT, as manifested by upfield shifts of aromatic protons in the binary adducts versus their free components, whereas 2D nuclear Overhauser effect spectroscopy (NOESY) spectra suggest coupling between dithiolate donor protons with nitrofluorenone acceptor protons, in correlation with the solid-state stacking. The NMR spectra also show significant peak broadening, indicating some paramagnetism verified by magnetic susceptibility data. Solid-state absorption spectra reveal further red shifts and increased relative intensities of DACT bands for the solid adducts vs solution, suggesting cooperativity of the DACT phenomenon in the solid state, as further substantiated by νC-O and νN-O IR bands and solid-state tight-binding computational analysis.

High dielectric constant aluminum oxide (Al(2)O(3)) is frequently used as the gate oxide in high electron mobility transistors and the impact of its deposition by radio frequency (RF) magnetron sputtering on the structural and electrical properties of multilayer epitaxial graphene (MLG) grown by graphitization of silicon carbide (SiC) is reported. Micro-Raman spectroscopy and temperature dependent Hall mobility measurements reveal that the processing induced changes to the structural and electrical properties of the MLG can be minimal when the oxide deposition conditions are optimal. High-resolution transmission electron microscopy (HRTEM) analysis confirms that the Al(2)O(3)/MLG interface is relatively sharp and that our thickness approximation of the MLG using angle resolved x-ray photoelectron spectroscopy (ARXPS) is accurate. An interface trap density of 5.1 × 10(10) eV(-1) cm(-2) was determined using capacitance-voltage techniques. The totality of our results indicates that ARXPS can be used as a nondestructive tool to measure the thickness of MLG, and that RF sputtered Al(2)O(3) can be used as a high dielectric (high-k) constant gate oxide in multilayer graphene based transistor applications.

We report on the effect of oxygen vacancies on the defect-related emission and the electronic properties of In 2 O 3 nanowires. The nanowires were synthesized by vapor phase transport and had diameters ranging from 80-100 nm and lengths over 10-20 μm, with a growth direction of [0 0 1]. The as-grown nanowires connected in an FET type of configuration show n-type conductivity, which is ascribed to the presence of intrinsic defects like oxygen vacancies in the nanowire. The resistivity, transconductance, field effect mobility and carrier concentration of the In 2 O 3 nanowires were determined to be 1.82 × 10 −2 cm, 11.2 nS, 119 cm 2 V −1 s −1 and 4.89 × 10 17 cm −3 , respectively. The presence of oxygen vacancies was also confirmed by photoluminescence measurements, which show a strong UV emission peak at 3.18 eV and defect peaks in the visible region at 2.85 eV, 2.66 eV and 2.5 eV. We present a technique of post-growth annealing in O 2 environment and passivation with (NH 4 ) 2 S to reduce the defect-induced emission.

Battery electrodes in thin-film form are free of the binders used with traditional powder electrodes and present an ideal platform to obtain basic insight to the evolution of the electrode-electrolyte interface passivation layer, the formation of secondary phases, and the structural underpinnings of reversibility. This is particularly relevant to the not yet fully understood conversion electrode materials, which possess enormous potential for providing transformative capacity improvements in next-generation lithium-ion batteries. However, this necessitates an understanding of the electronic charge transport properties and band structure of the thin films. This work presents an investigation of the electron transport properties of iron fluoride (FeF2) thin-film electrodes for Li-ion batteries. FeF2 thin films were prepared by pulsed-laser deposition, and their phase purity was characterized by electron microscopy and diffraction. The grown materials are polycrystalline FeF2 with a P42/mnm crystallographic symmetry. Room-temperature Hall measurements reveal that as-deposited FeF2 is n-type: the Hall coefficients were negative, electron mobility was 0.33 cm2/(V s) and resistivity was 0.255 Ω cm. The electronic band diagram of FeF2 was obtained using a combination of ultraviolet photoelectron spectroscopy, photoluminescence, photoluminescence excitation and optical absorption, which revealed that FeF2 is a direct bandgap, n-type semiconductor whose band structure is characterized by a 3.4 eV bandgap, a workfunction of ∼4.51 eV, and an effective Fermi level that resides approximately 0.22 eV below the conduction band edge. We propose that the shallow donor levels at 0.22 eV are responsible for the measured n-type conductivity. The band diagram was used to understand electron transport in FeF2 thin film and FeF2-C composite electrodes.