Influential effects of π-spacers, alkyl side chains, and various processing conditions on the photovoltaic properties of alkylselenyl substituted benzodithiophene based polymers

Abstract

π-spacers and alkyl side chains play a key role in the optical, electrochemical, and photovoltaic properties of π-conjugated polymers. To investigate the collective effects of π-spacers, alkyl side chains, and various processing conditions on the photovoltaic properties, an array of four new low bandgap (LBG) π-conjugated polymers (P1–P4) was designed and synthesized for their application as donor materials in bulk heterojunction polymer solar cells (BHJ PSCs). These π-conjugated polymers contain a benzodithiophene (BDT) donor unit substituted with 2-ethylhexylselenyl or 2-hexyldecylselenyl as π-conjugated side chains and a dialkoxybenzothiadiazole (dialkoxyBT) electron deficient unit connected with thiophene or selenophene as π-spacers. Among the four polymers, the absorption spectra of P3 with the thiophene π-spacer showed a well enhanced vibronic shoulder peak between 620 and 650 nm, indicating that P3 possesses a strong interchain aggregation tendency and attains a planar backbone structure due to the non-covalent interactions arising between the sulfur atom in thiophene and the oxygen atom in dialkoxyBT. Under suitable device processing conditions optimized pristine PSCs of P3 showed a maximum power conversion efficiency (PCE) of 4.09%. After employing 1,8-diiodooctane as an additive, one of the PSC devices based on P2 displayed a PCE of 5.34%. The active layers of P1–P4 showed a positive response towards methanol treatment, especially the P3-based devices delivered an improved PCE of 5.63%, which was further assessed by electrical impedance spectroscopy. These findings in the current article provide a good specimen for efficiently fine tuning the optical and photovoltaic properties of π-conjugated polymers via varying the size of alkyl chains, π-spacer groups and device processing conditions for the imminent growth of LBG π-conjugated polymers.