Stefan T. Bromley

Single-crystal organic field-effect transistors based on dibenzo-tetrathiafulvalene

We report on the fabrication and characterization of field-effect transistors based on single crystals of the organic semiconductor dibenzo-tetrathiafulvalene (DB-TTF). We demonstrate that it is possible to prepare very-good-quality DB-TTF crystals from solution. These devices show high field-effect mobilities typically in the range 0.1–1?cm2/V?s. The temperature dependence was also studied revealing an initial increase of the mobility when lowering the temperature until it reached a maximum, after which the mobility decreased following a thermally activated behavior with activation energies between 50 and 60?meV. Calculations of the molecular reorganization energy and intermolecular transfer integrals for this material were also performed and are in agreement with the high mobility observed in this material.

Dramatic reduction of the oxygen vacancy formation energy in ceria particles: a possible key to their remarkable reactivity at the nanoscale

We address the formation of the energetically most favourable single oxygen vacancies in ceria nanoparticles (CeO2)n focusing on their size dependence. We study a series of structures with increasing number of CeO2 units (n = 21, 30, 40 and 80) that, according to well tested interatomic-potential calculations, approach the global minima for these particle sizes. The structures thus obtained are refined by means of density functional (DF) methods, modified by the on-site Coulomb correction. Subsequent DF calculations are performed to quantify and analyse the depletion of atomic O from the nanoparticles that results in the formation of a vacancy Ovac. We show that (i) removal of a low- (two-)coordinate O atom from ceria species requires the lowest energy, in line with evidence from other metal oxides; (ii) the depletion of such O atoms from the nanoparticles is strongly facilitated compared to extended (even irregular) surfaces; (iii) increase of the particle size is accompanied by a dramatic decrease of the Ovac formation energy, implying that at certain sizes this energy should reach a minimum; (iv) the size dependence of the Ovac formation energy is driven by the electrostatics, thus enabling the prediction of the most easily removable O atoms by analysing the distribution of the electrostatic potential in the pristine stoichiometric (vacancy-free) ceria systems. Our findings provide a key to rationalize the observed spectacularly enhanced reactivity of ceria nanostructures.

Point defects in ZnO

We have investigated intrinsic point defects in ZnO and extended this study to Li, Cu and Al impurity centres. Atomic and electronic structures as well as defect energies have been obtained for the main oxidation states of all defects using our embedded cluster hybrid quantum mechanical/molecular mechanical approach to the treatment of localised states in ionic solids. With these calculations we were able to explain the nature of a number of experimentally observed phenomena. We show that in zinc excess materials the energetics of zinc interstitial are very similar to those for oxygen vacancy formation. Our results also suggest assignments for a number of bands observed in photoluminescence and other spectroscopic studies of the material.

Dust formation in the oxygen-rich AGB star IK Tauri

Aims: We model the synthesis of molecules and dust in the inner wind of the oxygen-rich Mira-type star IK Tau by considering the effects of periodic shocks induced by the stellar pulsation on the gas and by following the non-equilibrium chemistry in the shocked gas layers between 1 R ⋆ and 10 R ⋆ . We consider a very complete set of molecules and dust clusters, and combine the nucleation phase of dust formation with the condensation of these clusters into dust grains. We also test the impact of increasing the local gas density. Our derived molecular abundances and dust properties are compared to the most recent observational data. Methods: A semi-analytical formalism based on parameterised fluid equations is used to describe the gas density, velocity, and temperature in the inner wind. The chemistry is described by using a chemical kinetic network of reactions and the condensation mechanism is described by a Brownian formalism. A set of stiff, ordinary, coupled differential equations is solved, and molecular abundances, dust cluster abundances, grain size distributions and dust masses are derived. Results: The shocks drive an active non-equilibrium chemistry in the dust formation zone of IK Tau where the collision destruction of CO in the post-shock gas triggers the formation of C-bearing species such as HCN and CS. Most of the modelled molecular abundances agree well with the latest values derived from Herschel data, except for SO 2 and NH 3 , whose formation may not occur in the inner wind. Clusters of alumina, Al 2 O 3 , are produced within 2 R ⋆ and lead to a population of alumina grains close to the stellar surface. Clusters of silicates (Mg 2 SiO 4 ) form at larger radii (r> 3R ⋆ ), where their nucleation is triggered by the formation of HSiO and H 2 SiO. They efficiently condense and reach their final grain size distribution between ~6 R ⋆ and 8 R ⋆ with a major population of medium size grains peaking at ~200 A. This two dust-shell configuration agrees with recent interferometric observations. The derived dust-to-gas mass ratio for IK Tau is in the range 1-6 × 10 -3 and agrees with values derived from observations of O-rich Mira-type stars. Conclusions: Our results confirm the importance of periodic shocks in chemically shaping the inner wind of AGB stars and providing gas conditions conducive to the efficient synthesis of molecules and dust by non-equilibrium processes. They indicate that the wind acceleration will possibly develop in the radius range 4-8 R ⋆ in IK Tau.

Kondo Effect in a Neutral and Stable All Organic Radical Single Molecule Break Junction

Organic radicals are neutral, purely organic molecules exhibiting an intrinsic magnetic moment due to the presence of an unpaired electron in the molecule in its ground state. This property, added to the low spin-orbit coupling and weak hyperfine interactions, make neutral organic radicals good candidates for molecular spintronics insofar as the radical character is stable in solid state electronic devices. Here we show that the paramagnetism of the polychlorotriphenylmethyl radical molecule in the form of a Kondo anomaly is preserved in two- and three-terminal solid-state devices, regardless of mechanical and electrostatic changes. Indeed, our results demonstrate that the Kondo anomaly is robust under electrodes displacement and changes of the electrostatic environment, pointing to a localized orbital in the radical as the source of magnetism. Strong support to this picture is provided by density functional calculations and measurements of the corresponding nonradical species. These results pave the way toward the use of all-organic neutral radical molecules in spintronics devices and open the door to further investigations into Kondo physics.

Exploring Ce3+/Ce4+ cation ordering in reduced ceria nanoparticles using interionic-potential and density-functional calculations

The performance of atomistic calculations using interionic potentials has been examined in detail with respect to the structures and energetic stabilities of ten configurational isomers (i.e., distinct Ce3+/Ce4+ cationic orderings) of a low energy octahedral ceria nanoparticle Ce19O32. The outcome of these calculations is compared with the results of corresponding density-functional (DF) calculations employing local and gradient corrected functionals with an additional corrective onsite Coulombic interaction applied to the f-electrons (i.e., LDA+U and GGA+U, respectively). Strikingly similar relative energy ordering of the isomers and atomic scale structural trends (e.g., cation-cation distances) are obtained in both the DF and interionic-potential calculations. The surprisingly good agreement between the DF electronic structure calculations and the relatively simple classical potentials is not found to be due to a single dominant interaction type but is due to a sensitive balance between long range electrostatics and local bonding contributions to the energy. Considering the relatively high computational cost and technical difficulty involved in obtaining charge-localized electronic solutions for reduced ceria using DF calculations, the use of interionic potentials for rapid and reliable preselection of the most stable Ce3+/Ce4+ cationic orderings is of considerable benefit.

The effect of local environment on photoluminescence: A time-dependent density functional theory study of silanone groups on the surface of silica nanostructures

The optical absorption spectrum and lowest photoluminescence (PL) signal for silanone terminated silica nanostructures are studied using time-dependent density functional theory calculations on a range of realistic low energy silica nanocluster models. We show that the broad experimental absorption spectrum for silanone centers [V. A. Radtsig and I. M. Senchenya Russ. Chem. Bull. 45, 1849 (1996)] is most likely the result of a synergetic combination of inhomogeneous broadening, thermal broadening and the small energy differences between different excitations. We further demonstrate that upon relaxation of the excited state the excited electron and hole localize on only one silanone center, and that there is a clear and distinct link between the local environment of a silanone center and its absorption and PL spectra. Finally, we provide strong evidence that the silanone center does not have a double bond between the constituent silicon and oxygen atoms but rather can be probably more aptly described as the =Si(+)-O(-) charge-transfer species.

Dependence of charge transfer reorganization energy on carrier localisation in organic molecular crystals

Taking the organic molecular material dithiophene-tetrathiafulvalene (DT-TTF) as an example of a high mobility organic molecular material, we use density functional calculations to calculate the dependency of the reorganization energy associated with charge carrier transport on: (i) the geometric and electronic responsiveness of the local molecular crystal environment, and, (ii) the local spatial extent of the charge carrier. We find that in our most realistic extended models the charge transfer reorganization energy is strongly dependent on carrier localization. In particular, whereas highly localized carriers are found to be highly susceptible to their charge transfer efficiency being affected by changes in the local crystal environment, more delocalized carriers are better able to maintain their low reorganization energies. Considering that maintaining a relatively small charge transfer reorganization energy magnitude is an important factor in achieving high carrier mobilities, we suggest that those materials better able to sustain carriers with short-range thermally resistant intermolecular delocalisation should be sought for device applications.

The fate of optical excitations in small polyhedral ZnS clusters: A theoretical study of the excitation and localization of electrons in Zn4S4 and Zn6S6

We explore the excited state energy landscape of small polyhedral zinc sulfide clusters (Zn(4)S(4) and Zn(6)S(6)) using time-dependent density functional theory and correlated wave function based methods. We predict the optical absorption and photoluminescence spectra of the polyhedral clusters and demonstrate that, upon relaxation of the excited state, these nanostructures break symmetry and an electron and a hole localize on a small number of Zn (electron) and S (hole) centers. We further test several exchange-correlation potentials for their ability to recover the correlated wave function description of the excited state. Finally, we discuss how the degeneracy of excited states in nanostructures, such as those considered here, results in a Jahn-Teller distortion of the excited state geometry, and how numerical problems arising from this can be circumvented by starting the optimization of excited states from structures distorted along the ground state vibrational normal modes.

Octahedrality versus tetrahedrality in stoichiometric ceria nanoparticles

We predict that tetrahedral Ce(n)O(2n) nanoparticles <2 nm in size become more stable than those experimentally observed at larger sizes with truncated octahedral morphologies, based on global optimisation and density functional calculations.