Proceedings of 6th International Conference on Hybrid and Organic Photovoltaics (HOPV14)
Publication date: 1st March 2014
Dye-sensitized solar cells (DSSCs) using organic dyes are excellent candidates for next-generation solar cells, as they can be constructed from cheap and environmentally-friendly materials. However, organic dyes typically only absorb light over a narrow range, limiting the amount of sunlight able to be harvested.
To try to engineer panchromatic DSSCs, co-sensitization with two organic dyes having complementary absorption spectra has been employed.1 However, resonance energy transfer (RET) from the excited visible absorbing dye to the near-IR absorbing dye usually limits the increase in solar conversion efficiency that can be achieved. This arises because the electron injection efficiency of near-IR dye sensitizers is currently lower than that of visible dye sensitizers.
In this presentation, we demonstrate that RET between organic dyes on a co-sensitized metal-oxide surface can be suppressed by deliberately misaligning the excitation transition dipole moments of the dyes. This is achieved by exploiting the different chemical groups on each dye that are used to bind to the electrode and which govern the relative orientation of the two dyes on the surface.
The experiments are conducted in the gas phase by laser probing charged, dye-sensitized zirconia nanoparticles suspended in an ion trap and recording their time-resolved fluorescence decay curves.2 The presence of RET is determined by observing a decrease in the donor dye's excited state lifetime upon addition of the acceptor dye. The near-IR dye IR125 acts as the acceptor and attaches through two sulfonic acid binding groups, which causes it to lie parallel to the metal-oxide surface. Fast RET occurs when the D149 dye is used as the donor, as it possesses a rhodanine acetic acid binding group that causes the dye to lie parallel to the surface. Alternatively, RET occurs much more slowly when the D35 dye is used as the donor, as it possesses a cyanoacrylic acid binding group that causes the dye to sit perpendicular to the surface. The results are supported by time-dependent density functional theory calculations, which are used to predict the structures and excitation/emission dipole moments of the dyes.
Overall, this design concept should help maximize the light-harvesting efficiency within co-sensitized DSSCs by helping insulate the donor dye’s excited state against RET, preserving its superior electron injection capacity (relative to the acceptor dye).
The resonance energy transfer (RET) rate between the D149-IR125 pair (top) is fast, whereas the rate between the D35-IR125 pair (bottom) is slow.
1. Yum, J-H.; Baranoff, E.; Wenger, S.; Nazeeruddin, Md. K.; Gratzel, M. Panchromatic engineering for dye-sensitized solar cells. Energy Environ. Sci. 2011, 4, 842-857. 2. Dryza, V.; Nguyen, J. L.; Kwon, T-E.; Wong, W. W. H.; Holmes, A. B.; Bieske, E. J. Photophysics and aggregation effects of a triphenylamine-based dye sensitizer on metal-oxide nanoparticles suspended in an ion trap. Phys. Chem. Chem. Phys. 2013, 15, 20326-20332.
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