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  • 1. Abid, Jean-Pierre
    et al.
    Abid, Mohamed
    Uppsala University, Disciplinary Domain of Science and Technology.
    Bauer, Christophe
    Girault, Hubert H.
    Brevet, Pierre-Francois
    Controlled reversible adsorption of core: Shell metallic nanoparticles at the polarized water/1,2-dichloroethane interface investigated by optical second-harmonic generation2007In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 111, no 25, p. 8849-8855Article in journal (Refereed)
    Abstract [en]

    We report the observation of the reversible adsorption of core-shell gold-silver nanoparticles at the polarized water/1,2-dichloroethane interface using the nonlinear optical technique of surface second-harmonic generation. This study unambiguously demonstrates the excellent stability against aggregation of these core-shell nanoparticles, namely, gold core nanoparticles coated with silver layers of variable thickness, in the presence of an electrolyte salt like lithium chloride. Furthermore, it is also demonstrated that the adsorption of the nanoparticles is reversible by modulating the applied potential at water/1,2-dichloroethane interface. The analysis of these results is performed within the Debye-Huckel approximation of the electrostatic interactions between the nanoparticles. This approach shows that the stability of core-shell nanoparticles can be attributed to the formation of a silver oxide layer at the Surface of the particles.

  • 2.
    Agrios, Alexander G.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Low-temperature TiO2 Films for Dye-sensitized Solar Cells: Factors Affecting Energy Conversion Efficiency2008In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 112, no 27, p. 10021-10026Article in journal (Refereed)
    Abstract [en]

    Semiconductor films prepd. by electrostatic layer-by-layer deposition can be used to fabricate dye-sensitized solar cells after low-temp. treatment (150 DegC). However, the resulting photocurrent is much less than when the film is sintered at 500 DegC. The difference in short-circuit current is a factor of 2.2 with the Ru-based dye N719 and is 3.5 with the org. dye D5. The photocurrent at a given wavelength is proportional to the light-harvesting efficiency, charge injection effciency, and charge collection efficiency. Sintered films take up more than 60% more of either dye than unsintered films and therefore absorb more photons. Electron injection is hindered in unsintered films due to a conduction band edge potential 100 mV more neg. than in a sintered electrode. Addnl. injection effects could be due to adsorption of the dye to polymer rather than to TiO2 in unsintered films, although our measurements were inconclusive on this point. Kinetic studies show electron transport times (ttr) an order of magnitude faster then electron lifetimes (te) in both sintered and unsintered electrodes. Furthermore, a Li+ insertion expt. shows that both films have good elec. connectivity between TiO2 nanoparticles. Unsintered films thus exhibit efficient charge transport despite the presence of polymer and the lack of heat treatment to induce necking.

  • 3. Ahmad, Y.
    et al.
    Dubois, M.
    Guerin, K.
    Hamwi, A.
    Fawal, Z.
    Kharitonov, A. P.
    Generalov, A. V.
    Klyushin, A. Yu.
    Simonov, K. A.
    V.A. Fock Institute of Physics, St. Petersburg State University, St. Petersburg 198504, Russia.
    Vinogradov, Nikolay A.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics. V.A. Fock Institute of Physics, St. Petersburg State University, St. Petersburg 198504, Russia.
    Zhdanov, I. A.
    V.A. Fock Institute of Physics, St. Petersburg State University, St. Petersburg 198504, Russia.
    Preobrajenski, A. B.
    MAX-lab, Lund University, Box 118, 22100 Lund, Sweden.
    Vinogradov, A. S.
    V.A. Fock Institute of Physics, St. Petersburg State University, St. Petersburg 198504, Russia.
    NMR and NEXAFS Study of Various Graphite Fluorides2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 26, p. 13564-13572Article in journal (Refereed)
    Abstract [en]

    Graphite fluorides with different structural types (CyF)(n) (y = 2.5, 2, and 1) and room temperature graphite fluorides were studied by solid state,NMR and NEXAFS. Data extracted from those two techniques are complementary, providing information about the C-F bonding and the hybridization character of the carbon atom valence states. The comparison of data obtained by different methods such as NMR, Raman, and X-ray absorption leads to similar conclusions regarding the chemical bonding in fluorographites. Several major configurations of fluorinated graphites are discussed, that is, planar sheets with mainly sp(2) hybridization in room temperature graphite fluorides and corrugated sheets with sp(3) hybridization in covalent high temperature graphite fluoride. Different references such as highly oriented pyrolytic graphite (HOPG), graphitized carbon nanodiscs (graph-CNDs) and nanodiamonds (NDs) have also been investigated for comparison.

  • 4. Alarcón, H.
    et al.
    Hedlund, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics, Physics I.
    Johansson, Erik M. J.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics, Physics I.
    Rensmo, Håkan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics, Physics I.
    Hagfeldt, Anders
    KTH, Fysikalisk kemi / Physical Chemistry.
    Boschloo, Gerrit K.
    KTH, Fysikalisk kemi / Physical Chemistry.
    Modification of nanostructured TiO2 electrodes by electrochemical Al3+ insertion: Effects on dye-sensitized solar cell performance2007In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 111, no 35, p. 13267-13274Article in journal (Refereed)
    Abstract [en]

    Nanostructured TiO2 films were modified by insertion with aluminum ions using an electrochemical process. After heat treatment these films were found suitable as electrodes in dye-sensitized solar cells. By means of a catechol adsorption test, as well as photoelectron spectroscopy (PES), it was demonstrated that the density of Ti atoms at the metal oxide/electrolyte interface is reduced after Al modification. There is, however, not a complete coverage of aluminum oxide onto the TiO2, but the results rather suggest either the formation of a mixed Al−Ti oxide surface layer or formation of a partial aluminum oxide coating. No new phase could, however, be detected. In solar cells incorporating Al-modified TiO2 electrodes, both electron lifetimes and electron transport times were increased. At high concentrations of inserted aluminum ions, the quantum efficiency for electron injection was significantly decreased. Results are discussed at the hand of different models:  A multiple trapping model, which can explain slower kinetics by the creation of additional traps during Al insertion, and a surface layer model, which can explain the reduced recombination rate, as well as the reduced injection efficiency, by the formation of a blocking layer.

  • 5.
    Ali, Ehesan
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Materials Science.
    Sanyal, Biplab
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Materials Science.
    Oppeneer, Peter M.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Materials Science.
    Tuning the Magnetic Interaction between Manganese Porphyrins and Ferromagnetic Co Substrate through Dedicated Control of the Adsorption2009In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 113, no 32, p. 14381-14383Article in journal (Refereed)
    Abstract [en]

    We report, on the basis of density-functional theory+U (DFT+U) calculations that metalloporphyrins can adsorb on ferromagnetic metal surfaces in two distinct configurations. Two separate adsorption minima are obtained for manganese porphyrin (MnP) on Co from our DFT+U total energy calculations, which correspond to strong and weak adsorption strengths, respectively. By steering the nature of adsorption, we find that distinct chemical interactions as well as magnetic exchange interactions between the metalloporphyrin and the metal surface can be realized. We furthermore show that a switching of the MnP molecule's spin state can occur even for the weakly adsorbed case. This new discovery opens up prospects for engineering the chemical and magnetic exchange interaction in new functionalized spintronic materials.

  • 6. Amft, M.
    et al.
    Walle, L. E.
    Ragazzon, Davide
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Borg, A.
    Uvdal, P.
    Skorodumova, Natalia V.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Sandell, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    A Molecular Mechanism for the Water-Hydroxyl Balance during Wetting of TiO22013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 33, p. 17078-17083Article in journal (Refereed)
    Abstract [en]

    We show that the formation of the wetting layer and the experimentally observed continuous shift of the H2O-OH balance toward molecular water at increasing coverage on a TiO2(110) surface can be rationalized on a molecular level. The mechanism is based on the initial formation of stable hydroxyl pairs, a repulsive interaction between these pairs, and an attractive interaction with respect to water molecules. The experimental data are obtained by synchrotron radiation photoelectron spectroscopy and interpreted with the aid of density functional theory calculations and Monte Carlo simulations.

  • 7.
    Amorim, Rodrigo G.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory. Univ Fed Fluminense, Dept Fis, ICEx, Volta Redonda, RJ, Brazil..
    Rocha, Alexandre R.
    Univ Estadual Paulista, UNESP, Inst Fis Teor, Sao Paulo, Brazil..
    Scheicher, Ralph H.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Boosting DNA Recognition Sensitivity of Graphene Nanogaps through Nitrogen Edge Functionalization2016In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 34, p. 19384-19388Article in journal (Refereed)
    Abstract [en]

    One of the challenges for next generation DNA sequencing is to have a robust, stable, and reproducible nanodevice. In this work, we propose how to improve the sensing of DNA nucleobase using functionalized graphene nanogap as a solid state device. Two types of edge functionalization, namely, either hydrogen or nitrogen, were considered. We showed that, independent of species involved in the edge passivation, the highest-to-lowest order of the nucleobase transmissions is not altered, but the intensity is affected by several orders of magnitude. Our results show that nitrogen edge tends to p-dope graphene, and most importantly, it contributes with resonance states close to the Fermi level, which can be associated with the increased conductance. Finally, the translocation process of nucleobases passing through the nanogap was also investigated by varying their position from a certain height (from +3 to -3 angstrom) with respect to the graphene sheet to show that nitrogen-terminated sheets have enhanced sensitivity, as moving the nucleobase by approximately 1 angstrom reduces the conductance by up to 3 orders of magnitude.

  • 8.
    Andersson, M.
    et al.
    Chalmers University of Technology.
    Kiselev, A.
    Umeå University.
    Österlund, Lars
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Physics.
    Palmqvist, A E C
    Chalmers University of Technology.
    Microemulsion-mediated room-temperature synthesis of high-surface-area rutile and its photocatalytic performance2007In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 111, no 18, p. 6789-6797Article in journal (Refereed)
    Abstract [en]

    Nanosized titania having the rutile crystalline structure was synthesized at room temperature using a microemulsion-mediated system. The formed rutile particles had a diameter of 3 nm, which corresponds well with the droplet size of the water-in-oil microemulsion used for their preparation. The crystallinity was monitored by both X-ray diffraction (XRD) and electron diffraction, together with dark-field electron microscopy (TEM) and high-resolution TEM. The rutile had a high specific surface area (similar to 300 m(2)/g) according to N-2 adsorption and the BET equation. To our knowledge, this is the highest specific surface area ever reported for rutile. The rutile crystals aligned in a specific crystallographic direction forming elongated aggregates 200-1000 nm in size, as observed by TEM and high-resolution TEM. The titania formation was followed in situ using dynamic light scattering and UV-vis spectroscopy, and together with TEM and XRD performed on samples collected throughout the duration of the titania synthesis, the results gave support for a formation scheme involving the initial formation of amorphous titania followed by crystallization of rutile. The photocatalytic performance of the formed material was evaluated by in situ Fourier transform infrared spectroscopy and compared to that of a rutile sample having a lower specific surface area (similar to 40 m(2)/g). The TEM and formate adsorption experiments revealed that the high-surface-area rutile had a much higher fraction of (101) facets than the low-surface-area sample, which predominantly exposed (110) facets. In particular, a new bidentate formate (mu-formate) species bridge-bonded to the (101) facet could be identified with characteristic bands at 1547 and 1387 cm(-1). The photodegradation rate of this species was found to be similar to the mu-formate species on the (110) facet. However, the overall formate degradation rate was larger on the high-surface-area rutile sample because of a high concentration of the more readily photodegradable monodentate formate (eta(1)-formate) on that sample.

  • 9.
    Araujo, Rafael Barros Neves de Araujo
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy.
    Banerjee, Amitava
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy.
    Divulging the Hidden Capacity and Sodiation Kinetics of NaxC6Cl4O2 : A High Voltage Organic2017In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455Article in journal (Other academic)
  • 10.
    Araujo, Rafael Barros Neves de
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Banerjee, Amitava
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory. Royal Inst Technol KTH, Dept Mat & Engn, Appl Mat Phys, S-10044 Stockholm, Sweden..
    Divulging the Hidden Capacity and Sodiation Kinetics of NaxC6Cl4O2: A High Voltage Organic Cathode for Sodium Rechargeable Batteries2017In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 26, p. 14027-14036Article in journal (Refereed)
    Abstract [en]

    In the current emerging sustainable organic battery field, quinones are seen as one of the prime candidates for application in rechargeable battery electrodes. Recently, C6Cl4O2, a modified quinone, has been proposed as a high voltage organic cathode. However, the sodium insertion mechanism behind the cell reaction remained unclear due to the nescience of the right crystal structure. Here, the framework of the density functional theory (DFT) together with an evolutionary algorithm was employed to elucidate the crystal structures of the compounds NaxC6Cl4O2 (x = 0.5, 1.0, 1.5 and 2). Along with the usefulness of PBE functional to reflect the experimental potential, also the importance of the hybrid functional to divulge the hidden theoretical capacity is evaluated. We showed that the experimentally observed lower specific capacity is a result of the great stabilization of the intermediate phase Na1.5C6Cl4O2. The calculated activation barriers for the ionic hops are 0.68, 0.40, and 0.31 eV, respectively, for NaC6Cl4O2, Na1.5C6Cl4O2, and Na2C6Cl4O2. These results indicate that the kinetic process must not be a limiting factor upon Na insertion. Finally, the correct prediction of the specific capacity has confirmed that the theoretical strategy used, employing evolutionary simulations together with the hybrid functional framework, can rightly model the thermodynamic process in organic electrode compounds.

  • 11. Asano, Kohta
    et al.
    Westerwaal, Ruud J.
    Anastasopol, Anca
    Mooij, Lennard P. A.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Physics.
    Boelsma, Christiaan
    Ngene, Peter
    Schreuders, Herman
    Eijt, Stephan W. H.
    Dam, Bernard
    Destabilization of Mg Hydride by Self-Organized Nanoclusters in the Immiscible Mg-Ti System2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 22, p. 12157-12164Article in journal (Refereed)
    Abstract [en]

    Mg is an attractive hydrogen storage material not only because of its high gravimetric and volumetric hydrogen capacities but also because of it low material costs. However, the hydride of MgH2 is too stable to release hydrogen under moderate conditions. We demonstrate that the formation of nanometer-sized clusters of Mg reduces the stability of MgH2 by the interface energy effect in the immiscible Mg-Ti system. Ti-rich MgxTi1-x (x < 0.5) thin films deposited by magnetron sputtering have a hexagonal close packed (HCP) structure, which forms a face-centered cubic (FCC) hydride phase upon hydrogenation. Positron Doppler broadening depth profiling demonstrates that after hydrogenation, nanometer-sized MgH2 clusters are formed which are coherently embedded in an FCC TiH2 matrix. The P (pressure)-T (optical transmission) isotherms measured by hydrogenography show that these MgH2 clusters are destabilized. This indicates that the formation of nanometer-sized Mg allows for the development of a lightweight and cheap hydrogen storage material with a lower desorption temperature.

  • 12. Barrabes, Noelia
    et al.
    Foettinger, Karin
    Llorca, Jordi
    Dalinov, Anton
    Medina, Francesc
    Sa, Jacinto
    Hardacre, Christopher
    Rupprechter, Guenther
    Pretreatment Effect on Pt/CeO2 Catalyst in the Selective Hydrodechlorination of Trichloroethylene2010In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 114, no 41, p. 17675-17682Article in journal (Refereed)
  • 13.
    Bender, Philipp
    et al.
    Univ Cantabria, E-39005 Santander, Spain..
    Fock, Jeppe
    Tech Univ Denmark, DK-2800 Lyngby, Denmark..
    Frandsen, Cathrine
    Tech Univ Denmark, DK-2800 Lyngby, Denmark..
    Hansen, Mikkel F.
    Tech Univ Denmark, DK-2800 Lyngby, Denmark..
    Balceris, Christoph
    TU Braunschweig, D-38106 Braunschweig, Germany..
    Ludwig, Frank
    TU Braunschweig, D-38106 Braunschweig, Germany..
    Posth, Oliver
    Phys Tech Bundesanstalt, D-10587 Berlin, Germany..
    Wetterskog, Erik
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Physics.
    Bogart, Lara K.
    UCL, London W1S 4BS, England..
    Southern, Paul
    UCL, London W1S 4BS, England..
    Szczerba, Wojciech
    Bundesanstalt Mat Forsch & Prufung, D-12205 Berlin, Germany.;AGH Univ Sci & Technol, PL-30059 Krakow, Poland..
    Zeng, Lunjie
    Chalmers Univ Technol, S-41296 Gothenburg, Sweden..
    Witte, Kerstin
    Univ Rostock, D-18059 Rostock, Germany.;Micromod Partikeltechnol GmbH, D-18119 Rostock, Germany..
    Grüttner, Cordula
    Micromod Partikeltechnol GmbH, D-18119 Rostock, Germany..
    Westphal, Fritz
    Micromod Partikeltechnol GmbH, D-18119 Rostock, Germany..
    Honecker, Dirk
    Inst Laue Langevin, F-38042 Grenoble, France..
    Gonzalez-Alonso, David
    Univ Cantabria, E-39005 Santander, Spain..
    Fernandez Barquin, Luis
    Univ Cantabria, E-39005 Santander, Spain..
    Johansson, Christer
    RISE Acreo, S-40014 Gothenburg, Sweden..
    Relating Magnetic Properties and High Hyperthermia Performance of Iron Oxide Nanoflowers2018In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 5, p. 3068-3077Article in journal (Refereed)
    Abstract [en]

    We investigated, in depth, the interrelations among structure, magnetic properties, relaxation dynamics and magnetic hyperthermia performance of magnetic nanoflowers. The nanoflowers are about 39 nm in size, and consist of densely packed iron oxide cores. They display a remanent magnetization, which we explain by the exchange coupling between the cores, but we observe indications for internal spin disorder. By polarized small-angle neutron scattering, we unambiguously confirm that, on average, the nano flowers are preferentially magnetized along one direction. The extracted discrete relaxation time distribution of the colloidally dispersed particles indicates the presence of three distinct relaxation contributions. We can explain the two slower processes by Brownian and classical Neel relaxation, respectively. The additionally observed very fast relaxation contributions are attributed by us to the relaxation of disordered spins within the nanoflowers. Finally, we show that the intrinsic loss power (ILP, magnetic hyperthermia performance) of the nanoflowers measured in colloidal dispersion at high frequency is comparatively large and independent of the viscosity of the surrounding medium. This concurs with our assumption that the observed relaxation in the high frequency range is primarily a result of internal spin relaxation, and possibly connected to the disordered spins within the individual nanoflowers.

  • 14.
    Bhandary, Sumanta
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Penazzi, Gabriele
    Univ Bremen, BCCMS, D-28359 Bremen, Germany..
    Fransson, Jonas
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Frauenheim, Thomas
    Univ Bremen, BCCMS, D-28359 Bremen, Germany..
    Eriksson, Olle
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Sanyal, Biplab
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Controlling Electronic Structure and Transport Properties of Zigzag Graphene Nanoribbons by Edge Functionalization with Fluorine2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 36, p. 21227-21233Article in journal (Refereed)
    Abstract [en]

    In this work, we report a detailed study of the electronic structure and transport properties of mono- and difluorinated edges of zigzag graphene nanoribbons (ZGNR) using density functional theory (DFT). The calculated formation energies at 0 K indicate that the stability of the nanoribbons increases with the increase in the concentration of difluorinated edge C atoms along with an interesting variation of the energy gaps between 0.0 to 0.66 eV depending on the concentration. This gives a possibility of tuning the band gaps by controlling the concentration of F for terminating the edges of the nanoribbons. The DFT results have been reproduced by density functional tight binding method. Using the nonequilibrium Green functional method, we have calculated the transmission coefficients of several mono- and difluorinated ZGNR as a function of unit cell size and degree of homogeneous disorder caused by the random placement of mono and difluorinated C atoms at the edges.

  • 15.
    Bidermane, Ieva
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Lüder, Johann
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ahmadi, S.
    Materialfysik, KTH-Electrum.
    Grazioli, C.
    CNR-IOM, Laboratorio TASC.
    Bouvet, M.
    Institut de Chimie Moléculaire de l’Université de Bourgogne.
    Brena, Barbara
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Mårtensson, Niklas
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Puglia, Carla
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Witkowski, N.
    Institut des Nanosciences de Paris, UPMC.
    When the Grafting of Double Decker Phthalocyanines on Si(100)-2 × 1 Partly Affects the Molecular Electronic Structure2016In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 26, p. 14270-14276Article in journal (Refereed)
    Abstract [en]

    A combined X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and density functional theory (DFT) study has been performed to characterize the adsorbate interaction of lutetium biphthalocyanine (LuPc2) molecules on the Si(100)-2 × 1 surface. Large molecule–substrate adsorption energies are computed and are found to compete with the molecule–molecule interactions of the double decker molecules. A particularly good matching between STM images and computed ones confirms the deformation of the molecule upon the absorption process. The comparison between DFT calculations and XP spectra reveals that the electronic distribution in the two plateaus of the biphthalocyanine are not affected in the same manner upon the adsorption onto the silicon surface. This finding can be of particular importance in the implementation of organic molecules in hybrid devices.

  • 16.
    Björneholm, Olle
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Werner, Josephina
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Ottosson, Niklas
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Öhrwall, Gunnar
    Ekholm, Victor
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Winter, Bernd
    Unger, Isaak
    Söderström, Johan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Deeper Insight into Depth-Profiling of Aqueous Solutions Using Photoelectron Spectroscopy2014In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 50, p. 29333-29339Article in journal (Refereed)
    Abstract [en]

    X-ray photoelectron spectroscopy (XPS) is widely used to probe properties such as molecular stoichiometry, microscopic distributions relative to the surface by so-called "depth-profiling", and molecular orientation. Such studies usually rely on the core-level photoionization cross sections being independent of molecular composition. The validity of this assumption has recently been questioned, as a number of gas-phase molecules have been shown to exhibit photon-energy-dependent nonstochiometric intensity oscillations arising from EXAFS-like modulations of the photoionization cross section. We have studied this phenomenon in trichloroethanol in both gas phase and dissolved in water. The gas-phase species exhibits pronounced intensity oscillations, similar to the ones observed for other gas-phase molecules. These oscillations are also observed for the dissolved species, implying that the effect has to be taken into account when performing depth-profiling experiments of solutions and other condensed matter systems. The similarity between the intensity oscillations for gas phase and dissolved species allows us to determine the photoelectron kinetic energy of maximum surface sensitivity, ~100 eV, which lies in the range of pronounced intensity oscillations.

  • 17. Blomquist, J.
    et al.
    Walle, L. E.
    Uvdal, P.
    Borg, A.
    Sandell, A.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Materials Science, Surface and Interface Science. Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Water Dissociation on Single Crystalline Anatase TiO2(001) Studied by Photoelectron Spectroscopy2008In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 112, no 42, p. 16616-16621Article in journal (Refereed)
    Abstract [en]

    The adsorption of water on the anatase TiO2(001)-(4 x 1) surface is studied using synchrotron radiation-excited core level photoelectron spectroscopy. The coverage-dependent adsorption of water at low temperature is monitored and compared to the sequence obtained after heating of a water multilayer. Two adsorption phases of submonolayer coverage can be defined: Phase 1 consists only of dissociated water, observed as OH-groups. This phase is found at low coverage at low temperature (190 K) and is the only state of adsorbed water above similar to 230 K. The saturation coverage of phase 1 is consistent with dissociation on the 4-fold-coordinated Ti ridge atoms of the (4 x 1) surface reconstruction. Phase 2 is found at higher coverage, reached at lower temperature. It consists of a mixture of dissociated and molecular water with a ratio of 1:1 at 170 K. The molecular water is found to bond to the hydroxyl groups. The hydroxyl coverage of phase 2 is approximately 2 times that of phase 1. The results suggest that the OH and H2O species of phase 2 are confined to the ridges of the surface.

  • 18.
    Borges, J.
    et al.
    Univ Minho, Ctr Fis, Campus Gualtar, P-4710057 Braga, Portugal.;Czech Tech Univ, Fac Elect Engn, Dept Control Engn, Tech 2, Prague 6, Czech Republic.;Inst Pedro Nunes, Lab Ensaios Desgaste & Mat, Rua Pedro Nunes, P-3030199 Coimbra, Portugal.;Univ Coimbra, SEG CEMUC, Mech Engn Dept, P-3030788 Coimbra, Portugal..
    Pereira, R. M. S.
    Univ Minho, Ctr Fis, Campus Gualtar, P-4710057 Braga, Portugal.;Univ Minho, Ctr Matemat, Campus Gualtar, P-4710057 Braga, Portugal.;Univ Minho, Dept Matemat & Aplicacoes, Campus Gualtar, P-4710057 Braga, Portugal..
    Rodrigues, M. S.
    Univ Minho, Ctr Fis, Campus Gualtar, P-4710057 Braga, Portugal.;Inst Pedro Nunes, Lab Ensaios Desgaste & Mat, Rua Pedro Nunes, P-3030199 Coimbra, Portugal..
    Kubart, Tomas
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Electronics.
    Kumar, Saroj
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Electronics.
    Leifer, Klaus
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Electronics.
    Cavaleiro, A.
    Univ Coimbra, SEG CEMUC, Mech Engn Dept, P-3030788 Coimbra, Portugal..
    Polcar, T.
    Czech Tech Univ, Fac Elect Engn, Dept Control Engn, Tech 2, Prague 6, Czech Republic.;Univ Southampton, Natl Ctr Adv Tribol Southampton nCATS, Southampton SO17 1BJ, Hants, England..
    Vasilevskiy, M. I.
    Univ Minho, Ctr Fis, Campus Gualtar, P-4710057 Braga, Portugal.;City Univ Hong Kong, Dept Phys & Mat Sci, Hong Kong, Hong Kong, Peoples R China.;City Univ Hong Kong, CFP, Hong Kong, Hong Kong, Peoples R China..
    Vaz, F.
    Univ Minho, Ctr Fis, Campus Gualtar, P-4710057 Braga, Portugal..
    Broadband Optical Absorption Caused by the Plasmonic Response of Coalesced Au Nanoparticles Embedded in a TiO2 Matrix2016In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 30, p. 16931-16945Article in journal (Refereed)
    Abstract [en]

    The effect of Au nanopattides' (NPs) concentration, site, and spatial distribution within a TiO2 dielectric matrix on the localized surface plasmon resonance (LSPR) band characteristics was experimentally and theoretically studied. The results of the analysis of the Au NPs' size distributions allowed us to conclude that isolated NPs grow only up to 5 to 6 nm in site, even for the highest annealing temperature used. However, for higher volume fractions of Au, the coalescence of closely located NPs yields elongated clusters that are much larger in size and cause a considerable broadening of the LSPR band. This effect was confirmed by Monte Carlo modeling results. Coupled dipole equations were solved to find the electromagnetic modes of a supercell, where isolated and coalesced NPs were distributed, from which an effective dielectric function of the nanocomposite material was calculated and used to evaluate the optical transmittance and reflectance spectra. The modeling results suggested that the observed LSPR band broadening is due to a wider spectral distribution of plasmonic modes, caused by the presence of coalesced NPs (in addition to the usual damping effect). This is particularly important for detection applications via surface-enhanced Raman spectroscopy (SERS), where it is desirable to have a spectrally broad LSPR band in order:to favor the fulfillment of the conditions of resonance matching, to electronic transitions in detected species.

  • 19.
    Brena, Barbara
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics.
    Ojamae, Lars
    Surface effects and quantum confinement in nanosized GaN clusters: Theoretical predictions2008In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 112, no 35, p. 13516-13523Article in journal (Refereed)
    Abstract [en]

    The structure and the electronic properties of stoichiometric (GaN)(n) clusters (with 6 < ;= n < ;= 48) were investigated by means of quantum-chemical hybrid density functional theory (DFT) using the B3LYP functional. Particular emphasis was put on the investigation of the evolution of the physical properties of the clusters as a function of their size. Two types of model clusters were studied. Cage-type structures were found to be the most stable for smaller cluster sizes, whereas for larger sizes conformations cut out from the GaN wurtzite crystal were favorable. The study of the electronic structure shows that the energy gap of the clusters tends to become larger as the dimensions of the clusters increase. The vertical electronic absorption energies were calculated by means of time-dependent (TD) DFT. For such small clusters, probably due to the predominant amount of surface atoms, well-defined quantum confinement effects, as commonly observed in crystalline quantum dots, are not apparent.

  • 20.
    Broqvist, Peter
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Kullgren, Jolla
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Wolf, Matthew J.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    van Duin, Adri C. T.
    Hermansson, Kersti
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    ReaxFF Force-Field for Ceria Bulk, Surfaces, and Nanoparticles2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 24, p. 13598-13609Article in journal (Refereed)
    Abstract [en]

    We have developed a reactive force-field of the ReaxFF type for stoichiometric ceria (CeO2) and partially reduced ceria (CeO2-x). We describe the parametrization procedure and provide results validating the parameters in terms of their ability to accurately describe the oxygen chemistry of the bulk, extended surfaces, surface steps, and nanoparticles of the material. By comparison with our reference electronic structure method (PBE+U), we find that the stoichiometric bulk and surface systems are well reproduced in terms of bulk modulus, lattice parameters, and surface energies. For the surfaces, step energies on the (111) surface are also well described. Upon reduction, the force-field is able to capture the bulk and surface vacancy formation energies (E-vac), and in particular, it reproduces the E-vac variation with depth from the (110) and (111) surfaces. The force-field is also able to capture the energy hierarchy of differently shaped stoichiometric nanoparticles (tetrahedra, octahedra, and cubes), and of partially reduced octahedra. For these reasons, we believe that this force-field provides a significant addition to the method repertoire available for simulating redox properties at ceria surfaces.

  • 21.
    Butorin, Sergei. M.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics.
    Modin, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy.
    Vegelius, Johan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy.
    Kvashnina, Kristina O.
    European Synchrotron, CS40220, F-38043 Grenoble 9, France.;HZDR, Inst Resource Ecol, POB 510119, D-01314 Dresden, Germany..
    Shuh, David K.
    Lawrence Berkeley Natl Lab, Div Chem Sci, MS 70A1150,One Cyclotron Rd, Berkeley, CA 94720 USA..
    Probing Chemical Bonding in Uranium Dioxide by Means of High- Resolution X-ray Absorption Spectroscopy2016In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 51, p. 29397-29404Article in journal (Refereed)
    Abstract [en]

    A systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d(3/2) edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree of the 5f localization in UO2. The results support the covalent character of UO2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.

  • 22.
    Böhme, Solveig
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Philippe, Bertrand
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics.
    Edström, Kristina
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Nyholm, Leif
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Photoelectron Spectroscopic Evidence for Overlapping Redox Reactions for SnO2 Electrodes in Lithium-Ion Batteries2017In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 9, p. 4924-4936Article in journal (Refereed)
    Abstract [en]

    In-house and synchrotron-based photoelectron spectroscopy (XPSand HAXPES) evidence is presented for an overlap between the conversion andalloying reaction during the cycling of SnO2 electrodes in lithium-ion batteries(LIBs). This overlap resulted in an incomplete initial reduction of the SnO2 as wellas the inability to regenerate the reduced SnO2 on the subsequent oxidative scan.The XPS and HAXPES results clearly show that the SnO2 conversion reactionoverlaps with the formation of the lithium tin alloy and that the conversion reactiongives rise to the formation of a passivating Sn layer on the SnO2 particles. The latterlayer renders the conversion reaction incomplete and enables lithium tin alloy toform on the surface of the particles still containing a core of SnO2. The results alsoshow that the reoxidation of the lithium tin alloy is incomplete when the formationof tin oxide starts. It is proposed that the rates of the electrochemical reactions andhence the capacity of SnO2-based electrodes are limited by the lithium masstransport rate through the formed layers of the reduction and oxidations products.In addition, it is shown that a solid electrolyte interphase (SEI) layer is continuously formed at potentials lower than about 1.2 VLi+/Li during the first scan and that a part of the SEI dissolves on the subsequent oxidative scan. While the SEI was found tocontain both organic and inorganic species, the former were mainly located at the SEI surface while the inorganic species werefound deeper within the SEI. The results also indicate that the SEI dissolution process predominantly involves the organic SEIcomponents.

  • 23.
    Cappel, Ute B.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    Gibson, Elizabeth A.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    Boschloo, Gerrit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    Dye regeneration by spiro-MeOTAD in solid state dye-sensitized solar cells studied by photoinduced absorption spectroscopy and spectroelectrochemistry.2009In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 113, no 15, p. 6275-6281Article in journal (Refereed)
    Abstract [en]

    Photoinduced absorption (PIA) spectroscopy is presented as a tool for the systematic study of dye regeneration and pore filling in solid state dye-sensitized solar cells (DSC). Oxidn. potentials and extinction coeffs. for oxidized species of the perylene dye, ID28, on TiO2 and of the hole conductor, 2,2'7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-MeOTAD), were detd. by spectroelectrochem. The onset of oxidn. of a solid film of spiro-MeOTAD was found to be 0.15 V vs. Fc/Fc+ and extinction coeffs. of spiro-MeOTAD+ were found to be 33 000 M-1 cm-1 at 507 nm and 8500 M-1 cm-1 at 690 nm. Electrons in TiO2 films were shown to alter the ground-state absorption spectra of ID28 attached to TiO2. PIA measurements indicated a good contact between ID28 and spiro-MeOTAD for different spiro-MeOTAD concns. for both 2- and 6-micro m thick TiO2 films. We discuss the possibility of estg. the quality of pore filling from the positions of absorption peaks. Results suggested that with a spiro-MeOTAD concn. of 300 mg mL-1 in chlorobenzene, a uniform distribution of spiro-MeOTAD in the pores of the 6-micro m thick TiO2 film could be achieved.

  • 24.
    Cappel, Ute B.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    Karlsson, Martin H.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    Pschirer, G
    Eickemeyer, Felix
    Schoeneboom, Jan
    Erk, Peter
    Boschloo, Gerrit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry.
    A broadly absorbing perylene dye for solid-state dye-sensitized solar cells.2009In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 113, no 33, p. 14595-14597Article in journal (Refereed)
    Abstract [en]

    We present a new perylene sensitizer, ID 176, for dye-sensitized solar cells (DSCs). The dye has the capability for very high photocurrents due to strong absorption from 400 to over 700 rim. Photocurrents Of LIP to 9 mA cm(-2) were achieved in solid-state DSCs employing the hole conductor 2,2'7,7'-tetrakis-(NN-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-MeOTAD), with a conversion efficiency of 3.2%. In contrast, the sensitizer did not perform well in conjunction with liquid iodide/tri-iodide electrolytes, suggesting a difference in the injection and regeneration mechanisms in these two types of dye-sensitized solar cells.

  • 25.
    Cappel, Ute B.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Smeigh, Amanda L.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
    Plogmaker, Stefan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Surface and Interface Science.
    Johansson, Erik M. J.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Rensmo, Håkan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Surface and Interface Science.
    Hammarström, Leif
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science, Chemical Physics.
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Boschloo, Gerrit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Characterization of the Interface Properties and Processes in Solid State Dye-Sensitized Solar Cells Employing a Perylene Sensitizer2011In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 10, p. 4345-4358Article in journal (Refereed)
    Abstract [en]

    We recently reported on a perylene sensitizer, ID176, which performs much better in solid state dye-sensitized solar cells than in those using liquid electrolytes with iodide/tri-iodide as the redox couple (J. Phys. Chem. C2009, 113, 14595-14597). Here, we present a characterization of the sensitizer and of the TiO2/dye interface by UV-visible absorption and fluorescence spectroscopy, spectroelectrochemistry, photoelectron spectroscopy, electroabsorption spectroscopy, photoinduced absorption spectroscopy, and femtosecond transient absorption measurements. We report that the absorption spectrum of the sensitizer is red-shifted by addition of lithium ions to the surface due to a downward shift of the excited state level of the sensitizer, which is of the same order of magnitude as the downward shift of the titanium dioxide conduction band edge. Results from photoelectron spectroscopy and electrochemistry suggest that the excited state is largely located below the conduction band edge of TiO2 but that there are states in the band gap of TiO2 which might be available for photoinduced electron injection. The sensitizer was able to efficiently inject into TiO2, when a lithium salt was present on the surface, while injection was much less effective in the absence of lithium ions or in the presence of solvent. In the presence of the hole conductor 2,2-,7,7-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9-spirobifluorene (spiro-MeOTAD) and LiTFSI, charge separation was monitored by the emergence of a Stark shift of the dye in transient absorption spectra, and both injection and regeneration appear to be completed within 1 ps. Regeneration by spiro-MeOTAD is therefore several orders of magnitude faster than regeneration by iodide, and ID176 can even be photoreduced by spiro-MeOTAD.

  • 26. Chaudhary, Shilpi
    et al.
    Head, Ashley R.
    Sanchez-de-Armas, Rocio
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Tissot, Heloise
    Olivieri, Giorgia
    Bournel, Fabrice
    Montelius, Lars
    Ye, Lei
    Rochet, Francois
    Gallet, Jean-Jacques
    Brena, Barbara
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Schnadt, Joachim
    Real-Time Study of CVD Growth of Silicon Oxide on Rutile TiO2(110) Using Tetraethyl Orthosilicate2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 33, p. 19149-19161Article in journal (Refereed)
    Abstract [en]

    The interaction of the ruffle TiO2(110) surface with tetraethyl orthosilicate (TEOS) in the pressure range from UHV to 1 mbar as well as the TEOS-based chemical vapor deposition of SiO2 on the TiO2(110) surface were monitored in real time using near-ambient pressure X-ray photoelectron spectroscopy. The experimental data and density functional theory calculations confirm the dissociative adsorption of TEOS on the surface already at room temperature. At elevated pressure, the ethoxy species formed in the adsorption process undergoes further surface reactions toward a carboxyl species not observed in the absence of a TEOS gas phase reservoir. Annealing of the adsorption layer leads to the formation of SiO2, and an intermediate oxygen species assigned to a mixed titanium/silicon oxide is identified. Atomic force microscopy confirms the morphological changes after silicon oxide formation.

  • 27.
    Choudhuri, Indrani
    et al.
    Indian Inst Technol, Sch Basic Sci, Discipline Chem, Indore 452020, Madhya Pradesh, India..
    Patra, Nandini
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy. Indian Inst Technol, Ctr Mat Sci & Engn, Indore 452020, Madhya Pradesh, India..
    Mahata, Arup
    Indian Inst Technol, Sch Basic Sci, Discipline Chem, Indore 452020, Madhya Pradesh, India..
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory. Royal Inst Technol KTH, Dept Mat Sci & Engn, Appl Mat Phys, S-10044 Stockholm, Sweden..
    Pathak, Biswarup
    Indian Inst Technol, Sch Basic Sci, Discipline Chem, Indore 452020, Madhya Pradesh, India.;Indian Inst Technol, Ctr Mat Sci & Engn, Indore 452020, Madhya Pradesh, India..
    B-N@Graphene: Highly Sensitive and Selective Gas Sensor2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 44, p. 24827-24836Article in journal (Refereed)
    Abstract [en]

    We have performed density functional theory (DFT) calculations to study the gas (CO, CO2, NO, and NO2) sensing mechanism of pure and doped (B@, N@, and B-N@) graphene surfaces. The calculated adsorption energies of the various toxic gases (CO, CO2, NO, and NO2) on the pure and doped graphene surfaces show, doping improves adsorption energy and selectivity. The electronic properties of the B-N@graphene surfaces change significantly compared to pure and B@ and N@graphene surfaces, while selective gas molecules are adsorbed. So, we report B-N codoping on graphene can be highly sensitive and selective for semiconductor-based gas sensor.

  • 28. Chylarecka, D.
    et al.
    Kim, T. K.
    Tarafder, Kartick
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Mueller, K.
    Goedel, K.
    Czekaj, I.
    Waeckerlin, C.
    Cinchetti, M.
    Ali, Md E.
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy.
    Piamonteze, C.
    Schmitt, F.
    Wuestenberg, J. -P
    Ziegler, C.
    Nolting, F.
    Aeschlimann, M.
    Oppeneer, Peter
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ballav, N.
    Jung, T. A.
    Indirect Magnetic Coupling of Manganese Porphyrin to a Ferromagnetic Cobalt Substrate2011In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 4, p. 1295-1301Article in journal (Refereed)
    Abstract [en]

    The coupling mechanism of magnetic molecules to ferromagnetic surfaces is of scientific interest to design and tune molecular spintronic interfaces utilizing their molecular and surface architecture. Indirect magnetic coupling has been proposed earlier on the basis of density functional theory +U (DFT+U) calculations, for the magnetic coupling of manganese(II) porphyrin (MnP) molecules to thin Co films. Here we provide an experimental X-ray magnetic circular dichroism (XMCD) spectroscopy and scanning tunneling microscopy (STM) study of manganese(III) tetraphenylporphyrin chloride (MnTPPCl) on rough (exhibiting a high density of monatomic steps) and smooth (exhibiting a low density of monatomic steps) thin Co films grown on a Cu(001) single crystal toward the assessment of the magnetic coupling mechanism. After deposition onto the surface, MnTPPCl molecules were found to couple ferromagnetically to both rough and smooth Co substrates. For high molecular coverage, we observed higher XMCD signals at the Mn L-edges on the smooth Co substrate than on the rough Co substrate, as expected for the proposed indirect magnetic coupling mechanism on the basis of its predominance on the flat surface areas. In particular, DFT+U calculations predict a weak ferromagnetic molecule-substrate coupling only if the chloride ion of the MnTPPCl molecule orients away (Co-Mn-Cl) from the Co surface.

  • 29.
    Ciosek Högström, Katarzyna
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Hahlin, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Malmgren, Sara
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Gorgoi, Mihaela
    Helmholtz Zentrum Berlin Germany.
    Rensmo, Håkan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics.
    Edström, Kristina
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Aging of electrode/electrolyte interfaces in LiFePO4/graphite cells cycled with and without PMS additive2014In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 24, p. 12649-12660Article in journal (Refereed)
  • 30.
    Ciosek Högström, Katarzyna
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Malmgren, Sara
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Hahlin, Maria
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Rensmo, Håkan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics.
    Thébault, Frédéric
    Chalmers university of technology.
    Johansson, Patrik
    Chalmers university of technology.
    Edström, Kristina
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    The influence of PMS-additive on the electrode/electrolyte interfaces in LiFePO4/graphite Li-ion batteries2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 45, p. 23476-23486Article in journal (Refereed)
    Abstract [en]

    The influence of a film-forming additive, propargyl methanesulfonate (PMS), on electrochemical performance and electrode/electrolyte interface composition of LiFePO4/graphite Li-ion batteries has been studied. Combined use of in-house X-ray photoelectron spectroscopy (XPS) and soft and hard X-ray photoelectron spectroscopy (PES) enabled nondestructive depth profiling at four different probing depths in the 2-50 nm range. Cells cycled with PMS and LiPF6 in ethylene carbonate/diethyl carbonate (EC/DEC) were compared to a reference sample cycled without PMS. In the first cycle, PMS cells showed a higher irreversible capacity, which is explained by formation of a thicker solid electrolyte interphase (SEI). After three cycles, the SET thicknesses were determined to be 19 and 25 nm for the reference and PMS samples, respectively. After the initial cycling, irreversible losses shown by the PMS cells were lower than those of the reference cell. This could be attributed to a different SET composition and lower differences in the amount of lithium between lithiated and delithiated electrodes for the PMS sample. It was suggested that PMS forms a triple-bonded radical on reduction, which further reacts with the electrolyte. The PMS additive was shown to influence the chemical composition at the positive electrode/electrolyte interface. Thicker interface layers with higher C-O and smaller LiF contributions were formed on LiFePO4 cycled with PMS.

  • 31.
    Cochrane, Katherine A.
    et al.
    Univ British Columbia, Dept Chem, Vancouver, BC V6T 1Z1, Canada;Univ British Columbia, Stewart Blusson Quantum Matter Inst, Vancouver, BC V6T 1Z4, Canada.
    Roussy, Tanya S.
    Univ British Columbia, Dept Phys & Astron, Vancouver, BC V6T 1Z1, Canada.
    Yuan, Bingkai
    Univ British Columbia, Stewart Blusson Quantum Matter Inst, Vancouver, BC V6T 1Z4, Canada.
    Tom, Gary
    Univ British Columbia, Dept Phys & Astron, Vancouver, BC V6T 1Z1, Canada;Univ British Columbia, Stewart Blusson Quantum Matter Inst, Vancouver, BC V6T 1Z4, Canada.
    Marsell, Erik
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics. Univ British Columbia, Stewart Blusson Quantum Matter Inst, Vancouver, BC V6T 1Z4, Canada.
    Burke, Sarah A.
    Univ British Columbia, Dept Chem, Vancouver, BC V6T 1Z1, Canada;Univ British Columbia, Dept Phys & Astron, Vancouver, BC V6T 1Z1, Canada;Univ British Columbia, Stewart Blusson Quantum Matter Inst, Vancouver, BC V6T 1Z4, Canada.
    Molecularly Resolved Electronic Landscapes of Differing-Acceptor-Donor Interface Geometries2018In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, no 15, p. 8437-8444Article in journal (Refereed)
    Abstract [en]

    Organic semiconductors are a promising class of materials for numerous electronic and optoelectronic applications, including solar cells. However, these materials tend to be extremely sensitive to the local environment and surrounding molecular geometry, causing the energy levels near boundaries and interfaces essential to device function to differ from those of the bulk. Scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STM/STS) have the ability to examine both the structural and electronic properties of these interfaces on the molecular and submolecular scales. Here, we investigate the prototypical acceptor donor system, 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA)/copper(II) phthalocyanine (CuPc) using submolecularly resolved pixel-by-pixel STS to demonstrate the importance of subtle changes in interface geometry of prototypical solar cell materials. PTCDA and CuPc were sequentially deposited on NaCl bilayers to create lateral heterojunctions that were decoupled from the underlying substrate. Donor and acceptor states were observed to shift in opposite directions, suggesting an equilibrium charge transfer between the two. Narrowing of the gap energy compared to isolated molecules on the same surface is indicative of the influence of the local dielectric environment. Further, we find that the electronic state energies of both acceptor and donor are strongly dependent on the ratio and positioning of both molecules in larger clusters. This molecular-scale structural dependence of the electronic states of both interfacial acceptor and donor has significant implications for device design, where level alignment strongly correlates to device performance.

  • 32.
    Concas, G.
    et al.
    Univ Cagliari, Dipartimento Fis, SP Monserrato Sestu Km 0,700, I-09042 Monserrato, CA, Italy..
    Congiu, F.
    Univ Cagliari, Dipartimento Fis, SP Monserrato Sestu Km 0,700, I-09042 Monserrato, CA, Italy..
    Muscas, Giuseppe
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Physics.
    Peddis, D.
    Vinca Inst Nucl Sci, POB 522, Belgrade 11001, Serbia.;CNR, Ist Struttura Mat, I-00015 Monterotondo, RM, Italy..
    Determination of Blocking Temperature in Magnetization and Mössbauer Time Scale: A Functional Form Approach2017In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 30, p. 16541-16548Article in journal (Refereed)
    Abstract [en]

    We studied the temperature dependence of the magnetization in an ensemble of monodomain nanoparticles both with dc magnetometry and Mössbauer spectroscopy. The analytical form of the temperature dependence is given by the complementary cumulative distribution function. This allows to determine the magnetization blocking temperatures of the sample by a fitting procedure. It is possible to calculate the Mössbauer blocking temperature by a single spectrum and the dc magnetization blocking temperature by two points of the thermoremanent magnetization curve, thus with a large reduction of the experimental work. The method may be used for particles with not too strong interactions, such happens in the Fe28 sample and not for samples with strong interactions as N30; it may be used for interparticle interaction energies up to 2 yJ and not for energies larger than 60 yJ. This method of analysis of the data should be used in the future work concerning the thermoremanent magnetization and Mössbauer spectra of magnetic nanoparticles.

  • 33.
    Dahlstrand, Christian
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Jahn, Burkhard O.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Grigoriev, Anton
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Villaume, Sebastien
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics. Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC.
    Polyfulvenes: Polymers with "Handles" That Enable Extensive Electronic Structure Tuning2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 46, p. 25726-25737Article in journal (Refereed)
    Abstract [en]

    The fundamental electronic structure properties of substituted poly(penta)fulvenes and pentafulvene-based polymers are analyzed through qualitative molecular orbital (MO) theory combined with calculations at the B3LYP and HSE06 hybrid density functional theory (DFT) levels. We argue that the pentafulvene monomer unit has a unique character because electron density in the exocyclic C=C double bond can be polarized into and out of the five-membered ring, a feature that is not available to other more commonly used monomers. It is investigated how the energy gaps between the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO, respectively), as approximate band gaps, are influenced by exocyclic substitution, introduction of linker groups, benzannulation, and ring substitution. In particular, the exocyclic positions of the fulvene act as handles by which the electronic structure of the polymer can be tuned between the quinoid and fulvenoid valence bond isomers; electron-withdrawing exocyclic substituents lead to polyfulvenes in the quinoid form while those with electron-donating substituents prefer the fulvenoid. Taken together, the HOMO-LUMO gaps of polyfulvenes can be tuned extensively, varying in ranges 0.77-2.44 eV (B3LYP) and 0.35-2.00 eV (HSE06) suggesting that they are a class of polymers with highly interesting, yet nearly unexplored, properties.

  • 34.
    D'Amario, Luca
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Boschloo, Gerrit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Hammarström, Leif
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Tuning of Conductivity and Density of States of NiO Mesoporous Films Used in p-Type DSSCs2014In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 34, p. 19556-19564Article in journal (Refereed)
    Abstract [en]

    Nickel oxide has been used as the mesoporous electrode material for p-type dye sensitized solar cell (DSSC) for many years, but no high efficiency cells have been obtained yet. The poor results are commonly attributed to the lack of conductivity of the NiO film. In this paper we studied the electrical conduction of NiO mesoporous film with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). We used unsensitized NiO on FTO as an electrode with no dye adsorbed on the surface. Tests made with a DSSC device-like cell (FTO-Pt-I-/I-3(-)-NiO-FTO) showed a surprisingly high Faradaic current (20 mA/cm(-2) at 1 V), proving a good electrical conductivity of mesoporous NiO. We also used lithium as dopant to improve the electrical properties of the film. The Li-doping resulted in widening the inert (not conductive) window in the CV plot. The EIS analysis clarified that this behavior is due to a strong dependence of the valence band shape and position with respect to the Li-doping concentration. Our results show that DSSC performance does not need to be limited by the conductivity of mesoporous NiO, which encourages more effort in p-type DSSC research based on this material.

  • 35. Das, Supti
    et al.
    Hojberg, Jonathan
    Knudsen, Kristian Basthohn
    Younesi, Reza
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Johansson, Patrik
    Norby, Poul
    Vegge, Tejs
    Instability of Ionic Liquid-Based Electrolytes in Li-O-2 Batteries2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 32, p. 18084-18090Article in journal (Refereed)
    Abstract [en]

    Ionic liquids (ILs) have been proposed as promising solvents for Li-air battery electrolytes. Here, several ILs have been investigated using differential electrochemical mass spectrometry (DEMS) to investigate the electrochemical stability in a Li-O-2 system, by means of quantitative determination of the rechargeability (GER/ORR), and thereby the Coulombic efficiency of discharge and charge. None of the IL-based electrolytes are found to behave as needed for a functional Li-O-2 battery but perform better than commonly used organic solvents. Also the extent of rechargeability/reversibility has been found to be strongly dependent on the choice of IL cation and anion as well as various impurities.

  • 36. De Toro, Jose A.
    et al.
    Normile, Peter S.
    Lee, Su Seong
    Salazar, Daniel
    Cheong, Jian Liang
    Muniz, Pablo
    Riveiro, Jose M.
    Hillenkamp, Matthias
    Tournus, Florent
    Tamion, Alexandre
    Nordblad, Per
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Physics.
    Controlled Close-Packing of Ferrimagnetic Nanoparticles: An Assessment of the Role of Interparticle Superexchange Versus Dipolar Interactions2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 19, p. 10213-10219Article in journal (Refereed)
    Abstract [en]

    The fundamental question as to the relative importance of interparticle superexchange versus dipolar interaction between oxide magnetic particles in direct physical contact is addressed by examining the magnetic. properties of a series of compacted samples comprising identical maghemite particles (8 nm in diameter) coated by nonmagnetic shells (oleic acid or silica) of varying thickness that control the distance between the magnetic cores and hence the packing density (particle volume fraction). A remarkably narrow maghemite particle size distribution is established by electron microscopy and small-angle X-ray scattering. The series includes a sample made up of bare particles in a random-close-packed configuration (therefore in direct contact) that exhibits ideal superspin-glass behavior with a relatively high freezing transition temperature. It is shown that interparticle superexchange interactions between the nanoparticles in this sample play a minor role compared to classical dipolar interactions in establishing the collective, superspin-glass state. This follows from the freezing temperature of the most concentrated samples in the series (those with 0 <= shell thickness < 3 nm), which are found to vary in direct proportionality with the volume fraction of the maghemite cores and therefore with the strength of dipolar interactions.

  • 37.
    Difi, Siham
    et al.
    Univ Montpellier, CNRS, Inst Charles Gerhardt, UMR 5253, F-34095 Montpellier 5, France.;Univ Cadi Ayyad, Lab Chim Mat & Environm, Marrakech, Morocco..
    Saadoune, Ismael
    Univ Cadi Ayyad, Lab Chim Mat & Environm, Marrakech, Morocco..
    Sougrati, Moulay Tahar
    Univ Montpellier, CNRS, Inst Charles Gerhardt, UMR 5253, F-34095 Montpellier 5, France.;CNRS, FR 3459, Reseau Stockage Electrochim Energie RS2E, F-80039 Amiens, France..
    Hakkou, Rachid
    Univ Cadi Ayyad, Lab Chim Mat & Environm, Marrakech, Morocco..
    Edström, Kristina
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Lippens, Pierre-Emmanuel
    Univ Montpellier, CNRS, Inst Charles Gerhardt, UMR 5253, F-34095 Montpellier 5, France.;CNRS, FR 3459, Reseau Stockage Electrochim Energie RS2E, F-80039 Amiens, France..
    Mechanisms and Performances of Na1.5Fe0.5Ti1.5(PO4)(3)/C Composite as Electrode Material for Na-Ion Batteries2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 45, p. 25220-25234Article in journal (Refereed)
    Abstract [en]

    The properties, insertion mechanisms, and electrochemical performances of the Na1.5Fe0.5Ti1.5(PO4)(3)/C composite as electrode material for Na-ion batteries are reported. The composite was obtained by solid-state reaction and consists of porous secondary particles of submicron-sized particles coated by carbon. Detailed characterizations were performed by combining theoretical and experimental tools. This includes the determination of the crystal structure of Na1.5Fe0.5Ti1.5(PO4)(3) from both first-principles calculations and X-ray diffraction providing Na distribution over M1 and M2 interstitial sites, which is of importance for ionic conductivity. Na1.5Fe0.5Ti1.5(PO4)(3)/C was used as an electrode material at 2.2 V versus Na+/Na-0, exhibiting good Na-storage ability with a specific capacity of 125 mAh g(-1), close to the theoretical value, for the first discharge at C/10, good capacity retention, and Coulombic efficiency of 95% and 99.5% at the 60th cycle, respectively, and high power rate with a decrease of the specific capacity of only 14% from C/10 to 2C. These good performances have been related to the morphology of the composite and substitution of Fe for Ti, leading to an insertion mechanism that differs from that of NaTi2(PO4)(3). This mechanism was quantitatively analyzed from operand Fe-57 Mossbauer spectroscopy used for the first time in both galvanostatic and GITT modes.

  • 38. Ding, Bangfu
    et al.
    Qian, Haijiao
    Han, Chao
    Zhang, Junying
    Lindquist, Sten-Eric
    Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Physics.
    Wei, Bin
    Tang, Zilong
    Oxygen Vacancy Effect on Photoluminescence Properties of Self-Activated Yttrium Tungstate2014In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 118, no 44, p. 25633-25642Article in journal (Refereed)
    Abstract [en]

    A series of single-phase yttrium tungstate powders were synthesized through solid-state reaction under air or argon atmosphere. All powders showed broad band emission in the visible light region, and the argon-calcined samples presented strong near-infrared luminescence. Moreover, the long-wave excitation bands peaking at 340, 378, 380, 490, and 523 nm depended critically on the calcination atmosphere and temperature. The emergence of these new excitation bands was ascribed to different oxygen vacancy concentrations with the analysis of the first-principle calculation, Raman and X-ray absorption fine structure spectra. The oxygen vacancies caused the reduction of the average coordination number of tungsten, and the position of the localized energy band changed with the oxygen vacancy concentration. Finally, a schematic photoluminescence excitation model was proposed via anion and cation charge transfer. The obtained results promise to be very useful in interpreting self-activated tungstate luminescence mechanism. They can also serve as guide line for tuning the luminescence performance of yttrium tungstate and related materials.

  • 39. Dixit, M.
    et al.
    Maark, Tuhina Adit
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Ghatak, K.
    Ahuja, Rajeev
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Pal, S.
    Scandium-decorated MOF-5 as potential candidates for room-temperature hydrogen storage: A solution for the clustering problem in MOFs2012In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 116, no 33, p. 17336-17342Article in journal (Refereed)
    Abstract [en]

    Transition-metal-based systems show promising binding energy for hydrogen storage but suffer from clustering problem. The effect of light transition metal (M = Sc, Ti) decoration, boron substitution on the hydrogen storage properties of MOF-5, and clustering problem of metals has been investigated using ab initio density functional theory. Our results of solid-tate calculations reveal that whereas Ti clusters strongly Sc atoms do not suffer from this problem when decorating MOF-5. Boron substitution on metal-decorated MOF-5 enhances the interaction energy of both the metals with MOF-5. Sc-decorated MOF-5 shows a hydrogen storage capacity of 5.81 wt % with calculated binding energies of 20-40 kJ/mol, which ensures the room-temperature applicability of this hydrogen storage material.

  • 40.
    Dongare, Prateek
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry. Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA..
    Bonn, Annabell G.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry. Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA..
    Maji, Somnath
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry. Indian Inst Technol, Dept Chem, Hyderabad 502285, Telangana, India..
    Hammarström, Leif
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Analysis of Hydrogen-Bonding Effects on Excited-State Proton-Coupled Electron Transfer from a Series of Phenols to a Re(I) Polypyridyl Complex2017In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 23, p. 12569-12576Article in journal (Refereed)
    Abstract [en]

    In the present study of proton-coupled electron transfer (PCET) reactions, the excited-state of a fac-[(CO)(3)Re-I(bpy)(4,4'-bpy)](+) (bpy = 2,2'-bipyridine and 4,4'-bpy = 4,4'-bipyridine) complex was reductively quenched by a series of phenols. A variation of substituents on the phenols substantially alters their pK(a) and E degrees values and provides an opportunity to study photoinduced PCET as a function of their redox properties. Analyses of absorption spectral changes indicate that the phenols form a weak hydrogen bond with the pyridinic nitrogen of the 4,4'-bpy ligand in the ground-state, and ground-state association, constant (K-A) values were determined. This H-bonded adduct quenches the excited Re complex by PCET from the phenol, to form the reduced and,protonated Re complex. The KA values-obtained aid quantitative evaluation of the rate constant for the PCET reaction in the H-bonded, adduct. Thus, photophysical studies and Mechanistic analysis indicate that the reaction occurs via a concerted mechanistic pathway, for the unsubstituted phenol and phenols with electron-withdrawing subtituents. Furthermore; the magnitude of the quenching varies systematically with the proton-coupled potentials of the phenols and not their hydrogen-bonding strength (as reflected in K-A). This study is one of the first detailed analyses of intermolecular H-bonding between a self-assembling metal complex and a series of substituted phenols in an effort to study their relationship with the kinetic parameters in a photoinduced CPET reaction.

  • 41.
    Dunn, Halina K.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Westin, Per-Oskar
    Staff, Daniel R.
    Peter, Laurence M.
    Waker, Alison B.
    Boschloo, Gerrit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Physical and Analytical Chemistry, Physical Chemistry.
    Determination of the Electron Diffusion Length in Dye-Sensitized Solar Cells by Substrate Contact Patterning2011In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 28, p. 13932-13937Article in journal (Refereed)
    Abstract [en]

    A new method to estimate the electron diffusion length in dye-sensitized solar cells (DSCs) is presented. DSCs were fabricated on conducting glass substrates that were patterned by laser ablation of the fluorine-doped tin oxide coating to form parallel contact strips separated by uncontacted strips of the same width. The relative collection efficiency was measured as a function of the gap between the contact strips, which determines the lateral distance traveled by electrons to reach the contacts. To avoid complications arising from non-linear recombination kinetics, current measurements were performed using small amplitude perturbations of the electron density close to open circuit and the maximum power point to minimize electron density gradients in the film. One and two-dimensional solutions of the continuity equation for electron transport and back reaction predict that the relative collection efficiency should fall as spacing between the contact strips exceeds the electron diffusion length and electrons are lost by back electron transfer during transit to the contacts. Measurements of the relative collection efficiency were fitted to the predicted dependence of the collection efficiency on the spacing between the contact strips to obtain the value of the electron diffusion length. The diffusion length is found to increase with voltage both at open circuit and at the maximum power point.

  • 42.
    Ebadi, Mahsa
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Lacey, Matthew
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Brandell, Daniel
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
    Araujo, Carlos Moyses
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.
    Density Functional Theory Modeling the Interfacial Chemistry of the LiNO3 Additive for Lithium-Sulfur Batteries by Means of Simulated Photoelectron Spectroscopy2017In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 42, p. 23324-23332Article in journal (Refereed)
    Abstract [en]

    Lithium-sulfur (Li-S) batteries are considered candidates for next-generation energy storage systems due to their high theoretical specific energy. There exist, however, some shortcomings of these batteries, not least the solubility of intermediate polysulfides into the electrolyte generating a so-called "redox shuttle", which gives rise to self-discharge. LiNO3 is therefore frequently used as an electrolyte additive to help suppress this mechanism, but the exact nature of the LiNO3 functionality is still unclear. Here, density functional theory calculations are used to investigate the electronic structure of LiNO3 and a number of likely species (N-2, N2O, LiNO2, Li3N, and Li2N2O2) resulting from the reduction of this additive on the surface of Li metal anode. The N is X-ray photoelectron spectroscopy core level binding energies of these molecules on the surface are calculated in order to compare the results with experimentally reported values. The core level shifts (CLS) of the binding energies are studied to identify possible factors responsible for the position of the peaks. Moreover, solid phases of (cubic) c-Li3N and (hexagonal) alpha-Li3N on the surface of Li metal are considered. The N is binding energies for the bulk phases of Li3N and at the Li3N/Li interfaces display higher values as compared to the Li3N molecule, indicating a clear correlation between the coordination number and the CLS of the solid phases of Li3N.

  • 43. Edvinsson, Tomas
    et al.
    Li, Chen
    Pschirer, Neil
    Schoeneboom, Jan
    Eickemeyer, Felix
    Sens, Ruediger
    Boschloo, Gerrit
    Herrmann, Andreas
    Muellen, Klaus
    Hagfeldt, Anders
    Intramolecular charge-transfer tuning of perylenes: Spectroscopic features and performance in Dye-sensitized solar cells2007In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 111, no 42, p. 15137-15140Article in journal (Refereed)
  • 44. Ekström, Ulf
    et al.
    Ottosson, Henrik
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
    Norrman, Patrick
    Characterization of the Chemisorption of Methylsilane on a Au(1,1,1) Surface from the Silicon K- and L-Edge Spectra: A Theoretical Study Using the Four-Component Static Exchange Approximation2007In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 111, no 37, p. 13846-13850Article in journal (Refereed)
    Abstract [en]

    X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectra (NEXAFS) of methylsilane, isolated and chemisorbed to a Au(1,1,1) surface, are determined in the fully relativistic four-component static exchange approximationboth the K- and the L-edge of silicon are addressed in this investigation. In the fully chemisorbed structure, three H(Si) atoms have been cleaved off when Si binds in the hollow site of Au forming three Si−Au bonds of normal length. As due to the tri-coordinated chemisorption, the onsets of the K- and L-edge NEXAFS absorption bands occur some 2.0 and 2.5 eV lower in energy, respectively. The spin−orbit splittings in the silicon 2p-shell are not significantly changed due to adsorption. A partly chemisorbed methylsilane with only one H(Si) bond cleaved was also studied, and it is shown that the polarization dependence in the surface spectra contains details that can be used experimentally to identify the surface coordination of silicon. The red-shifts in the XPS silicon 1s (2p) spectra upon surface binding are 0.95 (0.65) and 1.15 (0.83) eV for the mono- and tricoordinated system, respectively.

  • 45.
    Ellis, Hanna
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Kaufmann Eriksson, Susanna
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Feldt, Sandra
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Gabrielsson, Erik
    KTH, Organisk kemi.
    Lohse, Peter
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
    Lindblad, Rebecka
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Sun, Licheng
    KTH, Organisk kemi.
    Rensmo, Håkan
    Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and condensed matter physics.
    Boschloo, Gerrit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Linker Unit Modification of Triphenylamine-based Organic Dyes for Efficient Cobalt Mediated Dye-Sensitized Solar Cells2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 41, p. 21029-21036Article in journal (Refereed)
    Abstract [en]

    Linker unit modification of donor-linker-acceptor-based organic dyes was investigated with respect to the spectral and physicochemical properties of the dyes. The spectral response for a series of triphenylamine (TPA)-based organic dyes, called LEG1-4, was shifted into the red wavelength region, and the extinction coefficient of the dyes was increased by introducing different substituted dithiophene units on the pi-conjugated linker. The photovoltaic performance of dye-sensitized solar cells (DSCs) incorporating the different dyes in combination with cobalt-based electrolytes was found to be dependent on dye binding. The binding morphology of the dyes on the TiO2 was studied using photoelectron spectroscopy, which demonstrated that the introduction of alkyl chains and different substituents on the dithiophene linker unit resulted in a larger tilt angle of the dyes with respect to the normal of the TiO2-surface, and thereby a lower surface coverage. The good photovoltaic performance for cobalt electrolyte-based DSCs found here and by other groups using TPA-based organic dyes with a cyclopentadithiophene linker unit substituted with alkyl chains was mainly attributed to the extended spectral response of the dye, whereas the larger tilt angle of the dye with respect to the TiO2-surface resulted in less efficient packing of the dye molecules and enhanced recombination between electrons in TiO2 and Co(III) species in the electrolyte.

  • 46.
    Ellis, Hanna
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Schmidt, Ina
    Carl von Ossietzky Univ Oldenburg, Inst Chem, Ctr Interface Sci, Fac Math & Nat Sci, D-26111 Oldenburg, Germany..
    Hagfeldt, Anders
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry. Ecole Polytech Fed Lausanne, Inst Chem Sci & Engn, Lab Photomol Sci, EPFL FSB ISIC LSPM, CH-1015 Lausanne, Switzerland.;King Abdulaziz Univ, Ctr Excellence Adv Mat Res, Jeddah 21589, Saudi Arabia..
    Wittstock, Gunther
    Carl von Ossietzky Univ Oldenburg, Inst Chem, Ctr Interface Sci, Fac Math & Nat Sci, D-26111 Oldenburg, Germany..
    Boschloo, Gerrit
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry. Uppsala Univ, Dept Chem, Ctr Mol Devices, Phys Chem,Angstrom Lab, SE-75120 Uppsala, Sweden..
    Influence of Dye Architecture of Triphenylamine Based Organic Dyes on the Kinetics in Dye-Sensitized Solar Cells2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 38, p. 21775-21783Article in journal (Refereed)
    Abstract [en]

    The impact of the dye architecture on the kinetics in the dyesensitized solar cell (DSC) was investigated for two structurally similar organic dyes, adsorbed adsorbed to a mesoporous TiO2 film. Differences in the HOMO and LUMO levels of the triphenylamine dyes D35 and D45 were negligible, indicating that the changes in kinetics of the electron transfer processes in the solar cells can be attributed to structural differences of the organic dyes. The electron transfer kinetics of various processes was investigated by scanning electrochemical microscopy (SECM), transient absorption spectroscopy (TAS), and impedance spectroscopy (IS). SECM was used for the first time to determine the rate constants of the regeneration (reduction) of a photooiddized organic dye by a oneelectron cobalt mediator. Both TAS and IS measurements showed differences in recombination of electrons in TiO2, with oxidized D35 and D45. D45 with its shorter dimethoxyphenyl units yielded faster recombination and regeneration than D35, as measured by SECM and TAS. The results of this study show that small details in the dye structure significantly affect the kinetics of organic triphenylamine dye based dye-sensitized solar cells.

  • 47.
    El-Zohry, Ahmed M.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Roca-Sanjuan, Daniel
    Zietz, Burkhard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Ultrafast Twisting of the Indoline Donor Unit Utilized in Solar Cell Dyes: Experimental and Theoretical Studies2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 5, p. 2249-2259Article in journal (Refereed)
    Abstract [en]

    Previous time-resolved measurements on D149, the most-studied dye of the indoline family, had shown a fast time-component of 20-40 ps that had tentatively been attributed to structural relaxation. Using femtosecond transient absorption, we have investigated the isolated indoline donor unit (i.e., without acceptor group) and found an ultrafast decay characterized by two lifetimes of 3.5 and 23 ps. Density functional theory calculations show p-bonding and p*-antibonding character of the central ethylene group for the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), respectively. The LUMO is localized on the flexible vinyl-diphenyl region of the donor unit and a twisting process is assumed to occur as a deactivation process for the excited molecule. This is confirmed by multireference second-order perturbation theory (CASSCF/CASPT2) calculations of the lowest-lying excited state, in which it is shown that torsion of the ethylene bond to 96 degrees and pyramidalization to ca. 100 degrees lead to a conical intersection with the ground state. Embedded in a plastic matrix, where double bond rotation is hindered, the decay is slowed down to nanoseconds. We have also investigated the dyes D102, D131, and D149, possessing the same indoline donor unit, by femtosecond transient absorption and found a similar decay component. The ca. 20 ps deactivation channel in D-family dyes is thus attributed to a twisting process of the donor unit. The fluorescence quantum yields of this unit and D149 were measured, and from comparison, the competition of the discovered twisting deactivation channel to the radiative decay of the excited indoline dyes could be confirmed. Blocking this deactivation channel is expected to further increase efficiency for the indoline dyes.

  • 48.
    El-Zohry, Ahmed M.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Roca-Sanjuán, Daniel
    Instituto de Ciencia Molecular, Universitat de València, P.O. Box 22085, ES-46071 València, Spain.
    Zietz, Burkhard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Ultrafast Twisting of the Indoline Donor Unit Utilized in Solar Cell Dyes: Experimental and Theoretical Studies2015In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 119, no 5, p. 2249-2259Article in journal (Refereed)
    Abstract [en]

    Previous time-resolved measurements on D149, the most-studied dye of the indoline family, had shown a fast time-component of 20–40 ps that had tentatively been attributed to structural relaxation. Using femtosecond transient absorption, we have investigated the isolated indoline donor unit (i.e., without acceptor group) and found an ultrafast decay characterized by two lifetimes of 3.5 and 23 ps. Density functional theory calculations show π-bonding and π*-antibonding character of the central ethylene group for the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), respectively. The LUMO is localized on the flexible vinyl-diphenyl region of the donor unit and a twisting process is assumed to occur as a deactivation process for the excited molecule. This is confirmed by multireference second-order perturbation theory (CASSCF/CASPT2) calculations of the lowest-lying excited state, in which it is shown that torsion of the ethylene bond to 96° and pyramidalization to ca. 100° lead to a conical intersection with the ground state. Embedded in a plastic matrix, where double bond rotation is hindered, the decay is slowed down to nanoseconds. We have also investigated the dyes D102, D131, and D149, possessing the same indoline donor unit, by femtosecond transient absorption and found a similar decay component. The ca. 20 ps deactivation channel in D-family dyes is thus attributed to a twisting process of the donor unit. The fluorescence quantum yields of this unit and D149 were measured, and from comparison, the competition of the discovered twisting deactivation channel to the radiative decay of the excited indoline dyes could be confirmed. Blocking this deactivation channel is expected to further increase efficiency for the indoline dyes.

  • 49.
    El-Zohry, Ahmed M.
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Zietz, Burkhard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Concentration and Solvent Effects on the Excited State Dynamics of the Solar Cell Dye D149: The Special Role of Protons2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 13, p. 6544-6553Article in journal (Refereed)
    Abstract [en]

    D149 is one of the best-performing metal-free, organic dyes for dye-sensitized solar cells. Excited state lifetimes strongly depend on the solvent used and have previously been reported to be between 100 and 700 ps, without any mechanistic explanation being given. We have earlier shown that photo-isomerization is one of several deactivation processes. Here, we report that lifetimes in certain solvents depend on concentration, even in very dilute (nanomolar) solutions. A detailed investigation of the concentration dependence enables us to assign a second, faster deactivation channel besides isomerization that reduces lifetimes further: a ground-state, hydrogen-bonded 1:1 complex of D149 with acids or interaction with protic solvents leads to excited state quenching, most probably through excited state proton transfer. This includes self-quenching caused by D149's own carboxylic group through intermolecular interaction, accounting for the concentration-dependent lifetimes. We are now able to dissect the complex excited state behavior into its components, allowing us to attribute rate constants to the isomerization and the excited-state proton transfer process. We are also able to explain the excited state of D149 in a wide range of environmental conditions, in the presence of acids/bases, at different concentrations as well as with varying temperatures. Furthermore, we determine the barrier for isomerization, a thermally activated process. The consequences of these effects on solar cells are discussed. Also we show that ultrafast techniques like femtosecond pump probe and upconversion inherently do not provide the required responsiveness for work with the concentration ranges required here, whereas single photon counting with its ultimate sensitivity is able to resolve the underlying processes.

  • 50.
    El-Zohry, Ahmed
    et al.
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Orthaber, Andreas
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
    Zietz, Burkhard
    Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
    Isomerization and Aggregation of the Solar Cell Dye D1492012In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 116, no 50, p. 26144-26153Article in journal (Refereed)
    Abstract [en]

    D149, a metal-free indoline dye, is one of the most promising sensitizers for dye-sensitized solar cells (DSSCs) and has shown very high solar energy conversion efficiencies of 9%. Effective electron injection from the excited state is a prerequisite for high efficiencies and is lowered by competing deactivation pathways. Previous investigations have shown surprisingly short-lived excited states for this dye, with maximum lifetime components of 100-720 ps in different solvents and less than 120 ps for surface-adsorbed D149. Using steady-state and time-resolved fluorescence, we have investigated the photochemical properties of D149 in nonpolar and polar solvents, polymer matrices, and adsorbed on ZrO2, partially including a coadsorbent. In solution, excitation to the S-2 state yields a product that is identified as a photoisomer. The reaction is reversible, and the involved double-bond is identified by NMR spectroscopy. Our results further show that lifetimes of 100-330 ps in the solvents used are increased to more than 2 ns for D149 in polymer matrices and on ZrO2. This is in part attributed to blocked internal motion due to steric constraint. Conversely, concentration-dependent aggregation leads to a dramatic reduction in lifetimes that can affect solar cell performance. Our results explain the unexpectedly short lifetimes observed previously. We also show that photochemical properties such as lifetimes determined in solution are different from the ones determined on semiconductor surfaces used in solar cells. The obtained mechanistic understanding should help develop design strategies for further improvement of solar cell dyes.

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