| 1. |
- Hahlin, Maria, 1975-
(författare)
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Electronic and Molecular Surface Structures of Dye-Sensitized TiO2 Interfaces
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The dye-sensitized solar cell is a promising solar cell technology. In these systems the key process for light to electricity conversion is molecular in nature and is initiated in dye molecules adsorbed at a semiconducting surface. This thesis focuses on the electronic and molecular surface structure of the dye/TiO2 interface, and the experimental results were obtained from surface sensitive X-ray based electron spectroscopic methods. Two families of dyes, triarylamine based organic dyes and ruthenium based inorganic dyes, were investigated. The effect of dye structural modications on the interfacial properties was studied, such as the surface concentrations, dye molecular surface orientation, molecular interactions, and energy level matching. Also, the impact of additional parameters such as the incorporation of coadsorbents and the solvents used for dye sensitization were studied and complementary photoelectrochemical characterization was used to demonstrate functional properties corresponding to changes in the molecular layers. The experiments provided information on how specic structural modications change the frontier electronic structure. The results also showed that the adsorption of the organic dye leads to submolecular electronic changes, and that the dye surface orientations in general favor effcient energy conversion. Moreover, effects of solvents and coadsorbents, on both energy level matching between the dye and the TiO2 substrate and the surfacemolecular structure were quantied.
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| 2. |
- Massel, Felix, 1986-
(författare)
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Anion redox processes in novel battery cathode materials investigated by soft X-ray spectroscopy
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presents experimental investigations of the electronic structure of emerging and novel cathode materials used in lithium- and sodium-ion batteries. The investigated materials include a range of oxide materials containing the elements nickel and manganese. Central goals are to find fundamental explanations for favorable, respectively, unfavorable electrochemical cycling behavior and to arrive at a better understanding of the roles that the different elemental constituents of the compounds play. The experiments are based on the application of X-ray Absorption Spectroscopy (XAS) and Resonant Inelastic X-ray Scattering (RIXS) in the soft X-ray region and have been performed at synchrotron radiation facilities such as The Advanced Light Source (USA), The Swiss Light Source (Switzerland) and SPring-8 (Japan). XAS and RIXS of spinel LiNi0.44Mn1.56O4 at the O K-edge as well as the Ni and Mn L-edges were measured for two different crystal structures, namely, transition-metal-ordered and -disordered, respectively. The results show that both Ni and O contribute strongly as redox centers for the charge compensation during electrochemical cycling. The Ni L-RIXS spectra show evidence of a more stable Ni--O bond in the disordered material. In the layered manganese oxide materials Li[Li0.2Ni0.2Mn0.6]O2, Na0.67[Mg0.28Mn0.72]O2, and Na0.78[Li0.25Mn0.75]O2, as well as the disordered Li1.9Mn0.95O2.05F0.95 one observes that reversible O redox leads to two distinct features in O K-RIXS. Both features resonate in a narrow incident energy range suggesting that localized O hole states are formed, one close to the elastic peak and the other as a strong emission peak at an energy loss of about 8 eV. These features appear reversibly on the voltage plateau of the charge-discharge curve and can be used to identify a certain type of O redox reactions.The work also includes investigations that compare two different compositions of the structurally related material Li2MnO3 grown epitaxially as thin films. Evidence is found for anionic activity during the initial cycle that is of a different kind than the above as no evidence for localized O holes is found. Instead, excess Li in the transition metal layer is shown to lead to a more rapid loss of covalency in the Mn--O bonds.In short, this work presents some of the first explorations into the role of different types of anionic redox centers in cathodes, by means of XAS and RIXS thereby also demonstrating the utility and power of synchrotron based techniques for gaining atomic-level understanding of battery electrode materials.
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| 3. |
- Oscarsson, Johan, 1984-
(författare)
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Towards Mixed Molecular Layers for Dye-Sensitized Solar Cells : A Photoelectron Spectroscopy Study
- 2016
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The increasing demand for renewable energy has led to substantial research on different solar cell technologies. The dye-sensitized solar cell (DSC) is a technology utilizing dye molecules for light absorption. Dye molecules are adsorbed to a mesoporous semiconductor surface and after light absorption in the dye, charge separation occurs at this interface. Traditionally, DSCs have used layers of single dye species, but in recent efforts to enhance power conversion efficiency, more complex molecular layers have been designed to increase the light absorption. For example, the most efficient DSCs use a combination of two dye molecules, and such dye co-adsorption is studied in this thesis.A key to highly efficient DSCs is to understand the dye/semiconductor interface from a molecular perspective. One way of gaining this understanding is by using an element specific, surface sensitive technique, such as photoelectron spectroscopy (PES).In this thesis, PES is used to understand new complex dye/semiconductor interfaces. Dyes adsorbed to semiconductor surfaces are analyzed using PES in terms of geometric and electronic surface structure. The investigations ultimately target the effects of co-adsorbing dyes with other dyes or co-adsorbents.PES shows that Ru dyes can adsorb in mixed configurations to TiO2. Co-adsorption with an organic dye affects the configuration of the Ru dyes. As a consequence, shifts in energy level alignment and increased dye coverage are observed. The dyes are affected at a molecular level in ways beneficial for solar cell performance. This is called collaborative sensitization and is also observed in todays most efficient DSC.Dye molecules are generally sensitive to high temperatures and the substantial decrease in power conversion efficiency after heat-treatment can be understood using PES. Furthermore, comparing two mesoscopic TiO2 morphologies used in DSCs show differences in trap state density in the band gap, explaining the photovoltage difference in DSCs comprising these morphologies. Using mixed molecular layers on NiO results in significant improvements of p-type DSC power conversion efficiency. PES shows that changed adsorption configuration contribute to this effect.This thesis shows that PES studies can be used to obtain insight into functional properties of complex DSC interfaces at a molecular level.
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| 4. |
- Anselmo, Ana Sofia, 1980-
(författare)
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The morphology of polyfluorene : fullerene blend films for photovoltaic applications
- 2011
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Polymer photovoltaic systems whose photoactive layer is a blend of a semiconducting polymer with a fullerene derivative in a bulk heterojunction configuration are amongst the most successful organic photovoltaic devices nowadays. The three-dimensional organization in these layers (the morphology) plays a crucial role in the performance of the devices. Detailed characterization of this organization at the nanoscale would provide valuable information for improving future material and architectural design and for device optimization.In this thesis, the results of morphology studies of blends of several polyfluorene copolymers (APFOs) blended with a fullerene derivative are presented. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy was combined with dynamic Secondary Ion Mass Spectrometry (dSIMS) for surface and in-depth characterization of the blend films. NEXAFS was performed using two different electron detection methods, partial (PEY) and total (TEY) electron yield, which provide information from different depth regimes. Quantitative compositional information was obtained by fitting the spectra of the blend films with a linear combination of the spectra of films of the pure components. In blends of APFO3 with PCBM in two different blend ratios (1:1 and 1:4 of polymer:fullerene) NEXAFS data show the existence of compositional gradients in the vertical direction for both blend ratios, with clear polymer enrichment of the free surface. A series of APFOs with systematic changes in the side-chains was studied and it was shown that those small modifications can affect polymer:fullerene interaction and induce vertical phase separation. Polymer-enrichment of the free surface was clearly identified, in accordance with surface energy minimization mechanisms, and a compositional gradient was revealed already in the first few nanometers of the surface of the blend films. dSIMS showed that this vertical phase separation propagates throughout the film. It was possible to determine that as the polar character of the polymer increases, and thus the polymer:fullerene miscibility is improved, the tendency for vertical phase separation becomes stronger.
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