Effect of Anchoring Group on Electron Injection and Recombination Dynamics in Organic Dye-Sensitized Solar Cells

Journal article, 2009

In the field of dye-sensitized solar cells, the number of different sensitizing dyes is increasing rapidly. To produce low-cost dyes, much work is being directed toward synthesizing all-organic, ruthenium-free dyes with high extinction coefficients and broad absorption bands with large solar spectrum overlap. One of the best dyes, the polyene-diphenylaniline dye D5L2A1, has a rather blue absorption with an IPCE onset at around 650 nm, but it still has an energy conversion efficiency of almost 6%. To increase the overlap with the solar spectrum, the cyanoacrylic acid anchoring group was changed to rhodanine-3-acetic acid in complex D5L2A3. This gave an IPCE onset at around 750 nm, but unfortunately, it also decreased the overall efficiency to a modest 1.7%. By femtosecond transient absorption, we show that the electron injections into TiO(2) for the two dyes are ultrafast and indistinguishable with our time resolution (< 200 fs). However, charge recombination is also ultrafast, with different fractions of a ca. 500-fs component for the two dyes. Yet, the fraction of the faster decay component is larger for D5L2A3 than for D5L2A1. Here, we provide an interpretation of the implications of changing anchoring group. We believe that a lack of electron density oil the binding oxygens of the D5L2A3 LUMO, due to the rhodanine group, promotes a higher probability for electron injection to short-lived surface trap states compared to the situation for the fully conjugated D5L2A1.