The synthesis of a series of tetrafluorine-substituted, wide-bandgap, small molecules consisting of various π-conjugated spacers (furan, thiophene, selenophene) between indacenodithiophene as the electron-donating core and the electron-deficient difluorobenzothiadiazole unit is reported and the effect of the π-conjugated spacers on the photovoltaic properties is investigated. The alteration of the π-conjugated spacer enables fine-tuning of the photophysical properties and energy levels of the small molecules, and allows the adjustment of the charge-transport properties, the morphology of the photoactive films, as well as their photovoltaic properties. Moreover, most of these devices exhibit superior device performances after CH₂Cl₂ solvent annealing than without annealing, with a high fill factor (0.70–0.75 for all cases). Notably, the devices based on the new molecule BIT4FTh (with thiophene as the spacer) show an outstanding PCE of 8.7% (with an impressive FF of 0.75), considering its wide-bandgap (1.81 eV), which is among the highest efficiencies reported so far for small-molecules-based solar cells. The morphologies of the photoactive layers with/without CH₂Cl₂ solvent annealing are characterized by atomic force microscopy, transmission electron microscopy and two-dimensional grazing incidence X-ray diffraction analysis. The results reported here clearly indicate that highly efficient small-molecules-based solar cells can be achieved through rational design of their molecular structure and optimization of the phase-separated morphology via an adapted solvent–vapor annealing process.

A series of tetrafluorine-substituted small molecules with a D₁-A-D₂-A-D₁ linear framework based on indacenodithiophene and difluorobenzothiadiazole is designed and synthesized for application as donor materials in solution-processed small-molecule organic solar cells. The impacts of thiophene π-bridge and multiple fluorinated modules on the photophysical properties, the energy levels of the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO), charge carrier mobility, the morphologies of blend films, and their photovoltaic properties as electron donor material in the photoactive layer are investigated. By incorporating multiple fluorine substituents of benzothiadiazole and inserting two thiophene spacers, the fill factor (FF), open-circuit voltage, and short-circuit current density are dramatically improved in comparison with fluorinated-free materials. With the solvent vapor annealing treatment, further enhancement in charge carrier mobility and power conversion efficiency (PCE) are achieved. Finally, a high PCE of 8.1% with very-high FF of 0.76 for BIT-4F-T/PC₇₁BM is achieved without additional additive, which is among one of the highest reported for small-molecules-based solar cells with PCE over 8%. The results reported here clearly indicate that high PCE in solar cells based small molecules can be significantly increased through careful engineering of the molecular structure and optimization on the morphology of blend films by solvent vapor annealing.

In this work, two rigid, multiple tetraphenylethene (TPE)-substituted, π-conjugated, snowflake-shaped luminophores BT and BPT were facilely synthesized by using a 6-fold Suzuki coupling reaction. These molecules are constructed based on the nonplanar structure of propeller-shaped hexaphenylbenzene (HPB) or benzene as core groups and TPE as end groups. As a result, they reserve the intrinsic aggregation-induced emission (AIE) property of the TPE moiety. Meanwhile, both fluorescence quantum yield and piezochromic behavior in the solid state can be tuned or switched by inserting the phenyl bridges through changing the twisting conformation. The more extended structure BPT showed a much stronger AIE effect and higher Φ_F,f in the solid state in comparison with that of BT. Furthermore, an excellent optical waveguide application of these molecules was achieved. However, the revisable piezofluorochromic behavior has only appeared when BT was ground using a pestle and treated with solvent.