We recently reported the high performing molecular donor for OPV devices based on a benzodithiophene core, a terthiophene bridge and a rhodamine acceptor (BTR) . 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.
 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
The power conversion efficiencies (PCEs) of bulk heterojunction organic photovoltaic (OPV) devices have been reported more than 10%. Recently, in our group, we have achieved a PCE of greater than 11% with an inverted device geometry (device area 0.1 cm2) using a ternary blend comprising, an organic donor polymer, small molecule, and PC71BM, as an active layer. However, the device performance of OSC suffers significant drop with the device area scaling up due to sheet resistance of transparent electrode. In this work, we have used a thin layer of metal grid on top of transparent electrode to reduce the sheet resistance. Using this strategy, we fabricated inverted organic photovoltaic devices with an active layer composed of a ternary blend of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-co-3-fluorothieno[3,4-b] thiophene-2-carboxylate] (PTB7-Th) and small molecule (BTR)1 as the donors and PC71BM as the acceptor and we have achieved the PCE of greater than 8% for square centimetre active area devices. We also studied the role of metal grid thickness as well as geometry and annealing of active layer on the performance of OSCs.
1. K. Sun, Z. Xiao, S. Lu, W. Zajaczkowski, W. Pisula, E. Hanssen, J. M. White, R. M. Williamson, J. Subbiah, J. Ouyang, A. B. Holmes, W. W. H. Wong, D. J. Jones, Nat. Commun. 2015. (DOI: 10.1038/ncomms7013).
Efficient conversion of solar energy to electricity in low-cost organic photovoltaic (OPV) devices requires the complex interplay between multiple processes and components over various length and time scales. Optimizing device morphology to ensure efficient exciton diffusion and charge transport as well as ensuring efficient charge photogeneration is necessary to achieve optimum performance in new materials. The conjugated polymer electron donor PFM (poly(9,9-diocetyluorene-co-bis-N,N-(4-methylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine)) and electron acceptor F8BT (poly[(9,9-di-n-octyluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)), comprise the novel triblock copolymer PFM-F8BT-PFM. This copolymer is designed to phase separate on the 20-30 nm scale, a domain size ideal for maximizing exciton collection at the donor-acceptor interface. Using steady-state and ultrafast spectroscopic characterization including high repetition rate transient absorption spectroscopy, the dynamics of charge and energy transfer of the component polymers and the triblock co-polymer have been investigated. The results demonstrate that for the homopolymers solvent dependent exciton transport processes dominate, while in the triblock copolymer solutions transient spectroscopy provides evidence for interfacial charge separation.