Influence of alkyne spacers on the performance of thiophene-based donors in bulk-heterojunction organic photovoltaic cells

The ever-increasing demand for renewable energy has led to the intensification of research focused upon har-nessing the abundant energy from sunlight. Solution processed organic solar cells fabricated using conjugated polymer donor materials dominated the early development of organic photovoltaics (OPV). More recently, organic solar cells fabricated using small molecule donors have become increasingly attractive due to the ad-vantages these systems have over their polymeric counterparts. These include reproducible synthesis and the ability to more accurately develop structure-activity relationships. Here, we report the synthesis of thiophene based small molecule donors that have been used to investigate the influence of alkyne pi-spacers on the optical, electronic and photovoltaic properties of solution-processable bulk-heterojunction (BHJ) organic OPV cells. Additionally, we compare the addition of 3,4-ethylenedioxythiophene (EDOT) units in place of the end-thiophene of these derivatives. We found that the compounds featuring alkyne moieties displayed poor charge transfer and blue-shifted UV-vis spectra, whereas the incorporation of the EDOT units increased charge transfer for the non-alkyne derivative resulting in red-shifted absorbance. DFT calculations predicted higher charge separation/mobility and lower charge generation for the compounds without alkyne units. Indeed, greater J(sc) values and higher PCEs were found for the compounds lacking alkyne spacers. EDOT containing compounds showed poor performance which is likely due to an unfavourable morphology and higher HOMO level, leading to lower Voc. Hence, the simplest 5T-1 molecule showed the highest performance of 3.24%, which is c.a. 1.6x that of the alkyne-containing 5TA-1 and c.a. 2.9x that of the EDOT-containing derivative. This study demonstrates that alkyne spacers can be detrimental to orbital interactions, charge transfer and OPV performance, and that the EDOT unit can be added to provide greater charge transfer due to its auxiliary donating ability. However, careful design is required to ensure higher V-oc values and a favourable morphology in thiophene-based solution-pro-cessable OPVs.

Automated summary

This study reports the synthesis of small molecule donors with alkyne spacers for solution-processable organic photovoltaic cells. It was found that compounds with alkyne moieties displayed poor performance, while the addition of EDOT units improved charge transfer. The study concluded that careful design is necessary to ensure higher V-oc values and a favorable morphology in thiophene-based OPVs.