Mixed (difluoro)phenylpyridine/(difluoro)phenylpyrazole tris-cyclometalated iridium complexes were prepared in order to study the effect of fluorination and the pyridine/pyrazole ratio on the emission and electrochemical properties. Increasing fluorination and replacement of pyridine by pyrazole both leads to a widening of the HOMO-LUMO gap and generally leads to a blue shift in emission.

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.

Doping of few layered 2H WS2 films with Nb by pulsed laser deposition (PLD) using ablation targets fabricated from WS2, S and Nb powders is reported. The undoped controls were n-type, exhibited a Hall mobility of 0.4 cm2/Vs, and characterized by a Fermi level at 1.41 eV from the valence band edge. The latter was determined using ultraviolet photoelectron spectroscopy. Films doped at 0.5 and 1.1 atomic percentages niobium were p-type, and characterized by Fermi levels at 0.31 eV and 0.18 eV from the valence band edge. X-ray photoelectron spectroscopy indicates that Nb substitutes on W lattice sites. With increased Nb doping, the hole sheet concentration increased from 3.9 × 1012 to 8.6 × 1013 cm−2, while the mobility decreased from 7.2 to 2.6 cm2/Vs, presumably due to increased ionized impurity scattering. The approach demonstrates the potential of PLD for controlled doping of transition metal dichalcogenides.

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