The prototypical organic-oxide interface: intra-molecular resolution of sexiphenyl on In2_2O3_3(111)

The performance of an organic-semiconductor device is critically determined by the geometric alignment, orientation, and ordering of the organic molecules. While an organic multilayer eventually adopts the crystal structure of the organic material, the alignment and configuration at the interface with the substrate/electrode material is essential for charge injection into the organic layer. This work focuses on the prototypical organic semiconductor para-sexiphenyl (6P) adsorbed on In$_2$O$_3$(111), the thermodynamically most stable surface of the material that the most common transparent conducting oxide, indium tin oxide (ITO) is based on. The onset of nucleation and formation of the first monolayer are followed with atomically-resolved scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Annealing to 200$^\circ$C provides sufficient thermal energy for the molecules to orient themselves along the high-symmetry directions of the surface, leading to a single adsorption site. The AFM data suggests a twisted adsorption geometry. With increasing coverage, the 6P molecules first form a loose network with poor long-range order. Eventually the molecules re-orient and form an ordered monolayer. This first monolayer has a densely packed, well-ordered (2$\times$1) structure with one 6P per In$_2$O$_3$(111) substrate unit cell, i.e., a molecular density of 5.64$\times$10$^{13}$ cm$^{-2}$

Bond angles for O-H defects in SnO2 from polarization properties of their vibrational modes

Infrared absorption experiments made with polarized light yield significant insights into the possible structures of one- and two-O-H defects in SnO2 that are produced by thermal annealing treatments. These polarized absorption results reveal that a two-O-H defect must involve symmetry-equivalent O-H sites and that the axes of both one- and two-O-H defects are 63 degrees-68 degrees from the c axis of the rutile structure. These O-H bond angles found by experiment restrict the microscopic defect structures that are possible and suggest structures associated with either a metal atom substituting for Sn or an interstitial metal atom (such as Sn)

Competing electronic states emerging on polar surfaces

Excess charge on polar surfaces of ionic compounds is commonly described by the two-dimensional electron gas (2DEG) model, a homogeneous distribution of charge, spatially-confined in a few atomic layers. Here, by combining scanning probe microscopy with density functional theory calculations, we show that excess charge on the polar TaO2 termination of KTaO3(001) forms more complex electronic states with different degrees of spatial and electronic localization: charge density waves (CDW) coexist with strongly-localized electron polarons and bipolarons. These surface electronic reconstructions, originating from the combined action of electron-lattice interaction and electronic correlation, are energetically more favorable than the 2DEG solution. They exhibit distinct spectroscopy signals and impact on the surface properties, as manifested by a local suppression of ferroelectric distortions

Surface chemistry on a polarizable surface: Coupling of CO with KTaO3(001)

Polarizable materials attract attention in catalysis because they have a free parameter for tuning chemical reactivity. Their surfaces entangle the dielectric polarization with surface polarity, excess charge, and orbital hybridization. How this affects individual adsorbed molecules is shown for the incipient ferroelectric perovskite KTaO3. This intrinsically polar material cleaves along (001) into KO- and TaO2-terminated surface domains. At TaO2 terraces, the polarity-compensating excess electrons form a two-dimensional electron gas and can also localize by coupling to ferroelectric distortions. TaO2 terraces host two distinct types of CO molecules, adsorbed at equivalent lattice sites but charged differently as seen in atomic force microscopy/scanning tunneling microscopy. Temperature-programmed desorption shows substantially stronger binding of the charged CO; in density functional theory calculations, the excess charge favors a bipolaronic configuration coupled to the CO. These results pinpoint how adsorption states couple to ferroelectric polarization

Annual Report on the Investigation of the LiCaAlF6:Eu Scintillator Family for Next Generation Neutron Detection

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Ultrafast disordering of vanadium dimers in photoexcited VO2

Time-resolved x-ray scattering can be used to investigate the dynamics of materials during the switch from one structural phase to another. So far, methods provide an ensemble average and may miss crucial aspects of the detailed mechanisms at play. Wall et al. used a total-scattering technique to probe the dynamics of the ultrafast insulator-to-metal transition of vanadium dioxide (VO2) (see the Perspective by Cavalleri). Femtosecond x-ray pulses provide access to the time- and momentum-resolved dynamics of the structural transition. Their results show that the photoinduced transition is of the order-disorder type, driven by an ultrafast change in the lattice potential that suddenly unlocks the vanadium atoms and yields large-amplitude uncorrelated motions, rather than occurring through a coherent displacive mechanism.Peer ReviewedPostprint (author's final draft