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Dye Bonding to TiO2 In Situ Attenuated Total Reflection Infrared.pdf

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Dye Bonding to TiO2 In Situ Attenuated Total Reflection Infrared

Dye Bonding to TiO2: In Situ Attenuated Total Reflection Infrared Spectroscopy Study, Simulations, and Correlation with Dye- Sensitized Solar Cell Characteristics Barbara Vo?lker,*,? Florian Wo?lzl,? Thomas Bu?rgi,*,§ and Dominic Lingenfelser? ?Robert Bosch GmbH, Robert-Bosch-Platz 1, 70839 Gerlingen, Germany ?Physikalisch-Chemisches Institut, Universitat? Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany §Department of Physical Chemistry, University of Geneva, 30 Quai Ernest-Ansermet, 1211 Geneva, Switzerland ABSTRACT: Processing dye-sensitized solar cells gains more and more importance as interest in industrial applications grows daily. For large-scale processing and optimizing manufacturing in terms of environmental acceptability as well as time and material saving, a detailed knowledge of certain process steps is crucial. In this paper we concentrate on the sensitizing step of production, i.e., the anchoring of the dye molecules onto the TiO2 semiconductor. A vacuum-tight attentuated total reflection infrared (ATR-IR) flow-through cell was developed, thus allowing measurements using a vacuum spectrometer to monitor infiltration of dye molecules into the porous TiO2 film in situ at high sensitivity. In particular, the influence of the anchor and backbone of perylene dye molecules as well as the influence of solvents on the adsorption process was investigated. The experiments clearly show that an anhydride group reacts much slower than an acid group. A significantly lower amount of anhydride dye can be adsorbed on the films. Ex situ transmission experiments furthermore indicate that the availability of OH groups on the TiO2 surface may limit dye adsorption. Also the backbone and base frame of the dye can influence the adsorption time drastically. Electrical cell characteristics correlate with the amount of adsorbed dye molecules determined by in situ ATR-IR measurements. The latter is also sensitive toward the diffusion of the dye through the porous l