Structure and optical bandgap relationship of π-conjugated systems.

• Main Authors: André Leitão Botelho, Yongwoo Shin, Jiakai Liu, Xi Lin
• Format: Article
• Language: English
• Published: Public Library of Science (PLoS) 2014-01-01
• Series: PLoS ONE
• Online Access: http://europepmc.org/articles/PMC3908919?pdf=render

In bulk heterojunction photovoltaic systems both the open-circuit voltage as well as the short-circuit current, and hence the power conversion efficiency, are dependent on the optical bandgap of the electron-donor material. While first-principles methods are computationally intensive, simpler model Hamiltonian approaches typically suffer from one or more flaws: inability to optimize the geometries for their own input; absence of general, transferable parameters; and poor performance for non-planar systems. We introduce a set of new and revised parameters for the adapted Su-Schrieffer-Heeger (aSSH) Hamiltonian, which is capable of optimizing geometries, along with rules for applying them to any [Formula: see text]-conjugated system containing C, N, O, or S, including non-planar systems. The predicted optical bandgaps show excellent agreement to UV-vis spectroscopy data points from literature, with a coefficient of determination [Formula: see text], a mean error of -0.05 eV, and a mean absolute deviation of 0.16 eV. We use the model to gain insights from PEDOT, fused thiophene polymers, poly-isothianaphthene, copolymers, and pentacene as sources of design rules in the search for low bandgap materials. Using the model as an in-silico design tool, a copolymer of benzodithiophenes along with a small-molecule derivative of pentacene are proposed as optimal donor materials for organic photovoltaics.