Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

Abstract

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt-naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt-anthracene} (PISD-ANT). A series of donor–acceptor (D–A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm² V⁻¹ s⁻¹ is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm² V⁻¹ s⁻¹. When these polymer semiconductors were used as a donor and PC₇₁BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.