Electron Transfer from Bi-Isonicotinic Acid Emerges upon Photodegradation of N3-Sensitized TiO2 Electrodes.

Abstract

The long-term stability of dye-sensitized solar cells (DSSCs) is determined to a large extent by the photodegradation of their sensitizers. Understanding the mechanism of light-induced decomposition of dyes sensitizing a mesoporous oxide matrix may therefore contribute to solutions to increase the life span of DSSCs. Here, we investigate, using ultrafast terahertz photoconductivity measurements, the evolution of interfacial electron-transfer (ET) dynamics in Ru(4,4'-dicarboxylic acid-2,2'-bipyridine)2(NCS)2 (N3) dye-sensitized mesoporous TiO2 electrodes upon dye photodegradation. Under inert environment, interfacial ET dynamics do not change over time, indicating that the dye is stable and photodegradation is absent; the associated ET dynamics are characterized by a sub-100 fs rise of the photoconductivity, followed by long-lived (≫1 ns) electrons in the oxide electrode. When the N3-TiO2 sample is exposed to air under identical illumination conditions, dye photodegradation is evident from the disappearance of the optical absorption associated with the dye. Remarkably, approximately half of the sub-100 fs ET is observed to still occur but is followed by very rapid (∼10 ps) electron-hole recombination. Laser desorption/ionization mass spectrometry, attenuated total reflection-Fourier transform infrared, and terahertz photoconductivity analyses reveal that the photodegraded ET signal originates from the N3 dye photodegradation product as bi-isonicotinic acid (4,4'-dicarboxylic acid-2,2'-bipyridine), which remains bonded to the TiO2 surface via either bidentate chelation or bridging-type geometry.