Theoretical Study of Electron Transfer Properties of Squaraine Dyes for Dye Sensitized Solar Cell

摘要

The environmental issues and high cost of Ru create many scientists to explore cheaper and safer sensitizer as alternative for dye sensitized solar cells (DSCs). Dyes play an important role in solar energy conversion efficiency. The squaraine (SQ) dyes has good spectral match with the solar spectra, therefore, SQ dyes have great potential for the applications in DSCs. SQ01_CA is an unsymmetrical SQ dye, reported by Gratzel and colleagues in 2007, featuring a D-π—spacer-A framework and has a carboxylic acid anchoring group. The electron donating ability of indolium in SQ01CA and SQ01CAA dyes is relatively weak, better performance may be achieved by introducing an additional donor moiety into indolium [1]. In this study, we investigate six unsymmetrical SQ dyes adsorbed on a (TiO2)_(38) cluster [2] using density functional theory (DFT) and time-dependent DFT to study electron transfer properties of squaraine dyes on their photophysical. SQ01_CA, WH-SQ01_CA, and WH-SQ02_CA use a carboxylic acid group as its electron acceptor. Furthermore, SQ01_CAA, WH-SQ01_CAA, and WH-SQ02_CAA use a cyanoacrylic acid group as its electron acceptor. WH-SQ01_CA and WH-SQ01_CAA have an alkyl, while WH-SQ02_CA and WH-SQ02CAA have alkoxyl substituted diarylamines to the indolium donor of sensitizer SQ01CA. Our calculations show with additional diarylamines in donor tail of WH-SQ02_CAA, the SQ dyes have red-shifted absorption and have slightly larger probability of electron density transferred to TiO2 moiety. Furthermore, an additional-CN group as electron a withdrawing group in the acceptor exhibits red-shifted absorption and enhances the electron density transferred to TiO2 and anchoring moiety after photo-excitation. The tendency of calculated probabilities of electron density being delocalized into TiO2 and driving force for excited-state electron injection of these studied SQ dyes is compatible with their experimentally observed.