Benzothiadiazole derivatives functionalized with two different (hetero)aromatic donor groups: synthesis and evaluation as TiO2 sensitizers for DSSCs

A series of benzothiadiazole-based push-pull heterocyclic systems were synthesized and characterized in order to study the variations induced by different aromatic and heterocyclic donor groups in the optical, electronic and photovoltaic properties of DSSCs prepared with the respective cyanoacetic acid derivatives. The organic sensitizers bear a 5-hexyl-2,2’-bithienyl or N,N-diphenylanilino donor moieties conjugated with a thienyl-benzothiadiazole spacer functionalized with the electron acceptor/anchoring cyanoacetic acid group. The solar cell based on TiO2 sensitized with the novel dye bearing the 5-hexyl-2,2’-bithienyl donor, exhibited a power conversion efficiency of 0.95 % due the inefficient electron injection. Co-adsorption studies of the same dye resulted in enhanced photovoltaic conversion efficiency of 2.49 %, which represents an improvement of cell efficiency of 260 %. The sensitizer bearing the N,N-diphenylanilino donor exhibited 4.51 % power conversion efficiency, that was further enhanced by co-sensitization to 5.22 % efficiency.Thanks are due to Fundação para a Ciência e Tecnologia (FCT) for a PhD grant to S. S. M. Fernandes (SFRH/BD/87786/2012) and FEDERCOMPETE for financial support through the CQ/UM (Ref. UID/QUI/ 00686/2013 and UID/QUI/0686/2016). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased within the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT. A. Pereira, D. Ivanou, and A. Mendes would like to acknowledge the European Commission through the Seventh Framework Programme, the Scientific Programme “Ideas” of the European Research Council for research and technological development as part of an Advanced Grant under grant agreement No 321315, which also partially funded this work.