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Langmuir. 2010 Jun 15;26(12):9575-83. doi: 10.1021/la100137u.

Further understanding of the adsorption mechanism of N719 sensitizer on anatase TiO2 films for DSSC applications using vibrational spectroscopy and confocal Raman imaging.

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Materials Engineering, McGill University, Montreal, Canada, H3A 2B2.


Vibrational spectroscopic studies of N719 dye-adsorbed TiO(2) films have been carried out by using SERRS, ATR-FTIR, and confocal Raman imaging. The high wavenumber region (3000-4000 cm(-1)) of dye adsorbed TiO(2) is analyzed via Raman and IR spectroscopy to investigate the role of surface hydroxyl groups in the anchoring mode. As a complementary technique, confocal Raman imaging is employed to study the distribution features of key dye groups (COO-, bipyridine, and C=O) on the anatase surface. Sensitized TiO(2) films made from two different nanocrystalline anatase powders are investigated: a commercial one (Dyesol) and our synthetic variety produced through aqueous synthesis. It is proposed the binding of the N719 dye to TiO(2) to occur through two neighboring carboxylic acid/carboxylate groups via a combination of bidentate-bridging and H-bonding involving a donating group from the N719 (and/or Ti-OH) units and acceptor from the Ti-OH (and/or N719) groups. The Raman imaging distribution of COO(-)(sym) on TiO(2) was used to show the covalent bonding, while the distribution of C=O mode was applied to observe the electrostatically bonded groups.


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