Vacancy Control in Acene Blends Links Exothermic Singlet Fission to Coherence

The fission of singlet excitons into triplet pairs in organic materials holds great technological promise, but the rational application of this phenomenon is hampered by a lack of understanding of its complex photophysics. Here, we use the controlled introduction of vacancies by means of spacer molecules in tetracene and pentacene thin films as a tuning parameter complementing experimental observables to identify the operating principles of different singlet fission pathways. Time-resolved spectroscopic measurements in combination with microscopic modelling enables us to demonstrate distinct scenarios, resulting from different singlet-to-triplet pair energy alignments. For pentacene, where fission is exothermic, coherent mixing between the photoexcited singlet and triplet-pair states is promoted by vibronic resonances, which drives the fission process with little sensitivity to the vacancy concentration. Such vibronic resonances do not occur for endothermic materials such as tetracene, for which we find fission to be fully incoherent; a process that is shown to slow down with increasing vacancy concentration

Using temperature dependent fluorescence to evaluate singlet fission pathways in tetracene single crystals

The temperature-dependent fluorescence spectrum, decay rate, and spin quantum beats are examined in single tetracene crystals to gain insight into the mechanism of singlet fission. Over the temperature range of 250 K-500 K, the vibronic lineshape of the emission indicates that the singlet exciton becomes localized at 400 K. The fission process is insensitive to this localization and exhibits Arrhenius behavior with an activation energy of 550 ± 50 cm-1. The damping rate of the triplet pair spin quantum beats in the delayed fluorescence also exhibits an Arrhenius temperature dependence with an activation energy of 165 ± 70 cm-1. All the data for T > 250 K are consistent with direct production of a spatially separated 1(T⋯T) state via a thermally activated process, analogous to spontaneous parametric downconversion of photons. For temperatures in the range of 20 K-250 K, the singlet exciton continues to undergo a rapid decay on the order of 200 ps, leaving a red-shifted emission that decays on the order of 100 ns. At very long times (≈1 µs), a delayed fluorescence component corresponding to the original S1 state can still be resolved, unlike in polycrystalline films. A kinetic analysis shows that the redshifted emission seen at lower temperatures cannot be an intermediate in the triplet production. When considered in the context of other results, our data suggest that the production of triplets in tetracene for temperatures below 250 K is a complex process that is sensitive to the presence of structural defects

Pressure- and Temperature-Dependent Inelastic Neutron Scattering Study of the Phase Transition and Phonon Lattice Dynamics in Para-Terphenyl

Inelastic neutron scattering has been performed on para-terphenyl at temperatures from 10 to 200 K and under pressures from the ambient pressure to 1.51 kbar. The temperature dependence of phonons, especially low-frequency librational bands, indicates strong anharmonic phonon dynamics. The pressure- and temperature-dependence of the phonon modes suggest a lack of phase transition in the region of 0-1.51 kbar and 10-30 K. Additionally, the overall lattice dynamics remains similar up to 200 K under the ambient pressure. The results suggest that the boundary between the ordered triclinic phase and the third solid phase, reported at lower temperatures and higher pressures, is out of the pressure and temperature range of this study