El-Zohry A.M.,Angstrom Laboratories |
Roca-Sanjuan D.,University of Valencia |
Zietz B.,Angstrom Laboratories
Journal of Physical Chemistry C | Year: 2015
Previous time-resolved measurements on D149, the most-studied dye of the indoline family, had shown a fast time-component of 20-40 ps that had tentatively been attributed to structural relaxation. Using femtosecond transient absorption, we have investigated the isolated indoline donor unit (i.e., without acceptor group) and found an ultrafast decay characterized by two lifetimes of 3.5 and 23 ps. Density functional theory calculations show π-bonding and π∗-antibonding character of the central ethylene group for the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), respectively. The LUMO is localized on the flexible vinyl-diphenyl region of the donor unit and a twisting process is assumed to occur as a deactivation process for the excited molecule. This is confirmed by multireference second-order perturbation theory (CASSCF/CASPT2) calculations of the lowest-lying excited state, in which it is shown that torsion of the ethylene bond to 96° and pyramidalization to ca. 100° lead to a conical intersection with the ground state. Embedded in a plastic matrix, where double bond rotation is hindered, the decay is slowed down to nanoseconds. We have also investigated the dyes D102, D131, and D149, possessing the same indoline donor unit, by femtosecond transient absorption and found a similar decay component. The ca. 20 ps deactivation channel in D-family dyes is thus attributed to a twisting process of the donor unit. The fluorescence quantum yields of this unit and D149 were measured, and from comparison, the competition of the discovered twisting deactivation channel to the radiative decay of the excited indoline dyes could be confirmed. Blocking this deactivation channel is expected to further increase efficiency for the indoline dyes. © 2015 American Chemical Society.
El-Zohry A.,Angstrom Laboratories |
Orthaber A.,Angstrom Laboratories |
Zietz B.,Angstrom Laboratories
Journal of Physical Chemistry C | Year: 2012
D149, a metal-free indoline dye, is one of the most promising sensitizers for dye-sensitized solar cells (DSSCs) and has shown very high solar energy conversion efficiencies of 9%. Effective electron injection from the excited state is a prerequisite for high efficiencies and is lowered by competing deactivation pathways. Previous investigations have shown surprisingly short-lived excited states for this dye, with maximum lifetime components of 100-720 ps in different solvents and less than 120 ps for surface-adsorbed D149. Using steady-state and time-resolved fluorescence, we have investigated the photochemical properties of D149 in nonpolar and polar solvents, polymer matrices, and adsorbed on ZrO2, partially including a coadsorbent. In solution, excitation to the S2 state yields a product that is identified as a photoisomer. The reaction is reversible, and the involved double-bond is identified by NMR spectroscopy. Our results further show that lifetimes of 100-330 ps in the solvents used are increased to more than 2 ns for D149 in polymer matrices and on ZrO2. This is in part attributed to blocked internal motion due to steric constraint. Conversely, concentration-dependent aggregation leads to a dramatic reduction in lifetimes that can affect solar cell performance. Our results explain the unexpectedly short lifetimes observed previously. We also show that photochemical properties such as lifetimes determined in solution are different from the ones determined on semiconductor surfaces used in solar cells. The obtained mechanistic understanding should help develop design strategies for further improvement of solar cell dyes. © 2012 American Chemical Society.