Effect of fluorine on the photovoltaic properties of 2,1,3-benzothiadiazole-based alternating conjugated polymers by changing the position and number of fluorine atoms

Fluorination is one of the most effective ways to manipulate molecular packing, optical bandgap and molecular energy levels in organic semiconductor materials. In this work, different number of fluorine atoms was introduced into the acceptor moiety 2,2 '-dithiophene linked 2,1,3-benzothiadiazole, utilizing the alkylthiophene modified dithieno[2,3-d:2 ',3 '-d ']benzo[1,2-b:4,5-b] (DTBDT) as the donor unit, three polymers: PDTBDT-0F-BTs, PDTBDT-2F-BTs and PDTBDT-6F-FBTs were synthesized. With the number of fluorine atoms in each repeat unit of polymers varying from 0 to 2 and then up to 6, PDTBDT-0F-BTs, PDTBDT-2F-BTs and PDTBDT-6F-FBTs exhibited gradually downshifted energy levels and improved dielectric constants (epsilon r) from 3.4 to 4.3 to 5.8, further successively increased charge transport mobilities. As a result, the power conversion efficiency (PCE) of the bulk heterojunction organic photovoltaic devices (BHJ-OPV) from the blend films of aforementioned polymers paired with PC71BM were gradually increased from 1.69 for PDTBDT-0F-BTs to 1.89 for PDTBDT-2F-BTs and then to 5.28 for PDTBDT-6F-FBTs. The results show that the continuous insertion of fluorine atoms into the repeating units of the benzothiadiazole conjugated polymer leads to the deepening of HOMO energy level, the increase of epsilon r and the increase of charge mobility, which improve the efficiency of charge transfer and electron collection, thus improving the photovoltaic performance of BHJ-OPV. Incorporation of fluorine atoms in conjugated polymers leads to an increase in charge mobility and dielectric constant, increasing the Pdiss value and power conversion efficiency and open circuit voltage of polymer bulk heterojunction photovoltaic cells.