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Title: Photoinduced excitation and charge transfer processes of organic dyes with siloxane anchoring groups: a combined spectroscopic and computational study
Authors: Castellucci, E.
Monini, M.
Bessi, M.
Iagatti, A.
Bussotti, L.
Sinicropi, Adalgisa 
Calamante, M.
Zani, L.
Basosi, Riccardo 
Reginato, G.
Mordini, A.
Foggi, P.
Di Donato, M.
Issue Date: 2017
Project: None 
Dye-sensitized solar cells (DSSCs) have attracted significant interest in the last few years as effective low-cost devices for solar energy conversion. We have analyzed the excited state dynamics of several organic dyes bearing both cyanoacrylic acid and siloxane anchoring groups. The spectroscopic properties of the dyes were studied both in solution and when adsorbed on a TiO2 film using stationary and time-resolved techniques, probing the sub-picosecond to nanosecond time interval. The comparison between the spectra registered in solution and on the solid substrate evidences different pathways for the energy and electron relaxation. The transient spectra of the TiO2-adsorbed dyes show the appearance of a long wavelength excited state absorption band, attributed to the cationic dye species, which is absent in the spectra measured in solution. Furthermore, the kinetic traces of the samples adsorbed on TiO2 film show a long decay component not present in solution which constitutes an indirect evidence of electron transfer between the dye and the semiconductor. The interpretation of the experimental results has been supported by theoretical DFT calculations of the excited state energies and by the analysis of molecular orbitals of the analyzed dye molecules.
ISSN: 1463-9084
DOI: DOI: 10.1039/C7CP01956D
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