Investigating the dielectric properties and exciton diffusion in C70 derivatives.

In recent years, the dielectric constant (εr) of organic semiconductors (OSCs) has been of interest in the organic photovoltaic (OPV) community due to its potential influence on the exciton binding energy. Despite progress in the design of high εr OSCs and the accurate measurement of the εr, the effects of the synthetic strategies on specific (opto)electronic properties of the OSCs remain uncertain. In this contribution, the effects of εr on the optical properties of five new C70 derivatives and [70]PCBM are investigated. Together with [70]PCBM, the derivatives have a range of εr values that depend on the polarity and length of the side chains. The properties of the singlet excitons are investigated in detail with steady-state and time-resolved spectroscopy and the exciton diffusion length is measured. All six derivatives show similar photophysical properties in the neat films. However, large differences in the crystallinity of the fullerene films influence the exciton dynamics in blend films. This work shows that design principles for OSCs with a higher εr can have a very different influence on the performance of traditional BHJ devices and in neat films and it is important to consider the neat film properties when investigating the optoelectronic properties of new materials for OPV.

Control over Kinetic and Thermodynamically Driven Pathways of Crystallization to Yield Cofacial and Slipped-Stack Dimers in Single Crystals.

Control over the molecular packing in the solid state is of utmost importance in regulating the bulk optical properties of organic semiconductors. The electronic coupling between the molecules makes it possible to improve the properties of the bulk materials. This work reports an example of control over the selective formation of polymorphic single crystals of donor-acceptor-type small-molecule compound 25TR by 1) kinetic or 2) thermodynamic course of crystallisation to yield slipped stack (S) and cofacial (C) dimers in the single crystals. The distinct optical characteristics of the C-dimer and S-dimer are summarised. Both forms show significant excitonic interactions in the solid state, and the S-dimeric form has strong yellowish orange fluorescence, whereas the C-dimeric form is non-fluorescent in the crystalline state. DFT calculations and differential scanning calorimetric experiments revealed that the C-dimer polymorph is the thermodynamically stable form with a free energy offset of 0.43 eV in comparison with the S-dimer. Interestingly, the thermodynamically driven non-fluorescent single crystal was found to be convertible to its fluorescent form irreversibly by thermal trigger. The charge-carrier-transport characteristics of these two polymorphs were computed by using the Marcus-Hush formalism. The computations of the charge-carrier-transport behaviour revealed that the S-dimer (25TR(R) ) is ambipolar, whereas the C-dimer (25TR(Y) ) is predominantly n-type.

Directed Self-Organization Ensured Enhancement of Charge Carrier Mobilities in a Star-Shaped Organic Semiconductor.

Controlled self-organization of organic semiconductor molecules into specifically desired architectures on substrates of interest is one of the most imperative challenges faced in the fabrication of high-performance organic electronic devices. Herein, we report the self-organization of a star-shaped molecule FDT-8 into a highly favored structure, namely, a vertical stack. Thermal annealing of films of FDT-8 deposited on PEDOT: PSS coated ITO substrates was observed to assist the organization of the molecules into columnar stacks. A significant enhancement in the hole (≈50-fold) and the electron (≈13-fold) carrier mobility was observed in single-carrier devices upon thermal annealing that could be attributed to the aforementioned self-organization. The ability of these molecules to spontaneously self-organize was utilized to fabricate bilayer light-emitting devices.