Proceedings Article | 17 November 2016
KEYWORDS: Liquid crystals, Chromophores, Crystals, Bridges, Liquids, Annealing, Molecular bridges, Rhodamine, Organic semiconductors, Assembly equipment
We recently reported the high performing molecular donor for OPV devices based on a benzodithiophene core, a terthiophene bridge and a rhodamine acceptor (BTR) [1]. In this work we optimized side-chain placement of a known chromophore by ensuring the thiophene hexyl side-chains are regioregular, which should allow the chromophore to lie flat. The unexpected outcome was a nematic liquid crystalline material with significantly improved performance (now 9.6% PCE), excellent charge transport properties, reduced geminate recombination rates and excellent performance with active layers up to 400nm. Three phase changes were indicated by DSC analysis with a melt to a crystalline domain at 175 oC, transition to a nematic liquid crystalline domain at 186 oC and an isotropic melt at 196 oC.
In our desire to better understand the structure property relationships of this class of p-type organic semiconductor we have synthesized a series of analogues where the length of the chromophore has been altered through modification of the oligothiophene bridge to generate, the monothiophene (BMR), the bisthiophene (BBR), the known terthiophene (BTR), the quaterthiophene (BQR) and the pentathiophene (BPR). BMR, BBR and BPR have clean melting points while BQR, like BTR shows a complicated series of phase transitions. Device efficiencies after solvent vapour annealing are BMR (3.5%), BBR (6.0%), BTR (9.3%), BQR (9.4%), and BPR (8.7%) unoptimised.
OPV devices with BTR in the active layer are not stable under thermal annealing, however the bridge extended BQR and BPR form thermally stable devices. We are currently optimising these devices, but initial results indicate PCEs >9% for thermally annealed devices containing BQR, while BPR devices have not yet been optimised and have PCEs > 8%. In order to develop the device performance we have included BQR in ternary devices with the commercially available PTB7-Th and we report device efficiencies of over 10.5%.
We are currently optimising device assembly and annealing conditions and relating these back to key materials properties.
I will discuss the development of these new materials, their materials properties, structural data, and optimised device performance. I will examination of chromophore length on the Nematic Liquid Crystalline properties and on materials development and performance resulting in materials with > 9% PCE in OPV.
[1] Sun, K.; Xiao, Z.; Lu, S.; Zajaczkowski, W.; Pisula, W.; Hanssen, E.; White, J. M.; Williamson, R. M.; Subbiah, J.; Ouyang, J.; Holmes, A. B.; Wong, W. W.; Jones, D. J., Nat. Commun. 2015, 6, 6013. DOI: 10.1038/ncomms7013
