0000000000680779
AUTHOR
Arkady Yartsev
Electron Transfer from the Singlet and Triplet Excited States of Ru(dcbpy)2(NCS)2into Nanocrystalline TiO2Thin Films
Time-resolved absorption spectroscopy was used to study the femtosecond and picosecond time scale electron injection from the excited singlet and triplet states of Ru(dcbpY)(2)(NCS)(2) (RuN3) into titanium dioxide (TiO2) nanocrystalline particle film in acetonitrile. The fastest resolved time constant of similar to30 fs was shown to reflect a sum of two parallel ultrafast processes, nonergodic electron transfer (ET) from the initially excited singlet state of RuN3 to the conduction band of TiO2 and intersystem crossing (ISC). The branching ratio of 1.5 between the two competing processes gives rate constants of 1/50 fs(-1) for ET and 1/75 fs(-1) for ISC. Following the ultrafast processes, a…
Photoinduced ultrafast dynamics of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films:The influence of sample preparation and experimental conditions
In most of the previous ultrafast electron injection studies of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films, experimental conditions and sample preparation have been different from study to study and no studies of how the differences affect the observed dynamics have been reported. In the present paper, we have investigated the influence of such modifications. Pump photon density, environment of the sensitized film (solvent and air), and parameters of the film preparation (crystallinity and quality of the film) were varied in a systematic way and the obtained dynamics were compared to that of a well-defined reference sample: Ru(dcbpy)2(NCS)2−TiO2 in acetonitrile. In some cases, …
A study of electron transfer in Ru(dcbpy)2(NCS)2 sensitized nanocrystalline TiO2 and SnO2 films induced by red-wing excitation.
Excited state dynamics and electron transfer from the Ru(dcbpy)2(NCS)2 (RuN3) sensitizer to semiconductor nanoparticles were studied using time-resolved femtosecond absorption spectroscopy. We found that excitation of the red wing of the absorption spectrum of the sensitizer populates the (3)MLCT state directly, both in solution and attached on semiconductor nanoparticle films. Electron injection is slowed down and becomes gradually less efficient as excitation moves towards red from the absorption maximum at 535 nm. At 675 nm the injection is non-exponential and characterized by 5, 30 and 180 ps time constants. The non-exponential electron injection observed is assigned to injection from a…
Photoinduced interfacial electron injection in RuN3–TiO2 thin films: Resolving picosecond timescale injection from the triplet state of the protonated and deprotonated dyes
Using femtosecond transient absorption spectroscopy we have studied light-induced electron injection from the sensitizer RuN3 and its partly deprotonated tetrabutylamonium salt to nano-structured TiO2 film. Previous studies have suggested significant differences in electron injection dynamics for these dyes and some results have indicated that aggregation of the sensitizer may lead to slow injection. By measuring transient absorption spectra and kinetics of RuN3 and RuN3-TBA in solution and attached to TiO2 film we show that the electron injection dynamics are very similar for the two forms of the dye and that aggregation has only moderate effects on the electron transfer dynamics. (c) 2008…