Browsing by Subject "thin-films"

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Pseudo Jahn-Teller Effect In The Origin Of Enhanced Flexoelectricity
(2015-01) Bersuker, Issac B.; Bersuker, Issac B.
The controversy between the theory and experiment in explaining the origin of enhanced flexoelectricity is removed by taking into account the pseudo Jahn-Teller effect (PJTE) which, under certain conditions, creates local dipolar distortions of dynamic nature, resonating between two or more equivalent orientations. The latter become nonequivalent under a strain gradient thus producing enhanced flexoelectricity: it is much easier to orient ready-made dipoles than to polarize an ionic solid. For BaTiO3, the obtained earlier numerical data for the adiabatic potential energy surface in the space of dipolar displacements in the Ti centers were used to estimate the flexoelectric coefficient integral in the paraelectric phase in a one-dimensional model with the strain gradient along the [111] direction: integral = -0.43 X 10(-6) Cm-1. This eliminates the huge contradiction between the experimental data of integral similar to mu Cm-1 for this case and the theoretical predictions (without the PJTE) of 3-4 orders-of-magnitude smaller values. Enhanced flexoelectricity is thus expected in solids with a sufficient density of centers that have PJTE induced dipolar instabilities. It explains also the origin of enhanced flexoelectricity observed in other solids, noticeable containing Nb perovskite centers which are known to have a PJTE instability, similar to that of Ti centers. The SrTiO3 crystal as a virtual ferroelectric in which the strain gradient eases the condition of PJTE polar instability is also discussed. (C) 2015 AIP Publishing LLC.
Rhodium Pyrazolate Complexes as Potential CVD Precursors
(2012-02) Rivers, Joseph H.; Anderson, Lauren J. D.; Starr, Cotton M. N.; Jones, Richard A.; Rivers, Joseph H.; Anderson, Lauren J. D.; Starr, Cotton M. N.; Jones, Richard A.
Reaction of 3,5-(CF3)(2)PzLi with [Rh(mu-Cl)(eta(2)-C2H4)(2)](2) or [Rh(mu-Cl)(PMe3)(2)](2) in Et2O gave the dinuclear complexes [Rh(eta(2)-C2H4)(2)(mu-3,5-(CF3)(2)-Pz)](2) (1) and [Rh-2(mu-Cl)(mu-3,5-(CF3)(2)-Pz) (PMe3)(4)] (2) respectively (3,5-(CF3)(2)Pz = bis-trifluoromethyl pyrazolate). Reaction of PMe3 with [Rh(COD)(mu-3,5-(CF3)(2)-Pz)](2) in toluene gave [Rh(3,5-(CF3)(2)-Pz)(PMe3)(3)] (3). Reaction of 1 and 3 in toluene (1 : 4) gave moderate yields of the dinuclear complex [Rh(PMe3)(2)(mu-3,5-(CF3)(2)-Pz)](2) (4). Reaction of 3,5-(CF3)(2)PzLi with [Rh(PMe3)(4)]Cl in Et2O gave the ionic complex [Rh(PMe3)(4)][3,5-(CF3)(2)-Pz] (5). Two of the complexes, 1 and 3, were studied for use as CVD precursors. Polycrystalline thin films of rhodium (fcc-Rh) and metastable-amorphous films of rhodium phosphide (Rh2P) were grown from 1 and 3 respectively at 170 and 130 degrees C, 0.3 mmHg in a hot wall reactor using Ar as the carrier gas (5 cc min(-1)). Thin films of amorphous rhodium and rhodium phosphide (Rh2P) were grown from 1 and 3 at 170 and 130 degrees C respectively at 0.3 mmHg in a hot wall reactor using H-2 as the carrier gas (7 cc min(-1)).
Synthesis and Structures of Co Bis-Trifluoromethylpyrazolate Complexes
(2013-04) Rivers, Joseph H.; Jones, Richard A.; Rivers, Joseph H.; Jones, Richard A.
Reactions of Co(PMe3)(3)Cl or CoCl2 with 3,5-(CF3)(2)-PzNa in hexane give Co(PMe3)(3)(3,5-(CF3)(2)-Pz) (1) and Co(PMe3)(3)(3,5-(CF3)(2)-Pz)(2) (2) respectively (3,5-(CF3)(2)-PzNa = sodium bis-trifluoromethylpyrazolate). Reaction of (3,5-(CF3)(2)-PzH) with Co(PMe3)(4) produces the unusual complex [cis-Co(PMe3)(4)H-2][Co(PMe3)(3,5-( CF3)(2)-Pz)(3)] (3) which formally contains a [Co(III)](+)[Co(II)](-) complex ion pair. Reaction of 3,5-(CF3)(2)-PzLi with an oxygenated suspension of CoCl2 and 3 equivalents of PMe3 gives (3,5-(CF3)(2)-Pz)(2)Co(mu-3,5-(CF3)(2)Pz)(mu-OPMe3)Li(OPMe3)(2) (4), while 2 reacts with LiOH to give [(PMe3)Co(mu-3,5-(CF3)(2)-Pz)(2)(mu(3)-OH)Li](2) (5). Both 2 and 3 react with O-2 in toluene solution to give Co(OPMe3)(2)(3,5-(CF3)(2)-Pz)(2) (6). All compounds have been characterized spectroscopically and by single crystal X-ray diffraction studies.