Harvesting near- and far-field plasmonic enhancements from large size gold nanoparticles for improved performance in organic bulk heterojunction solar cells

The high stability and strong coupling nature of gold nanoparticles (Au-NPs) than other metal counter parts have attracted the solar cell industry to pursue enhanced performances. Herein, we report on the improved performance of polymer bulk hetero-junction (BHJ) solar cells by the incorporation of large-size Au-NPs in the hole transport layer of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). To examine the reproducibility of the enhancement parameters, two different donor photoactive materials have been adapted and the role of larger-size (>70 nm, i.e. 71, 80, 87, 103 nm) Au-NPs in BHJ solar cells have been studied extensively. Significantly, when employing Au-NPs smaller than 80 nm, near-field coupling (localized surface plasmon resonance; LSPR) was prevalent, while the infusion of Au-NPs with sizes greater than 87 nm resulted in far-field scattering enhancement as the dominant effect, which was clearly determined using time resolved photo luminescence studies. The superior power conversion efficiency of 5.35% and 8.58% was achieved with PBDTTT-C: PC₆₁BM and PTB7: PC₇₁BM BHJs respectively, by employing 87 nm Au-NPs due to the balanced contribution of near- and far-field plasmonic effects, improved vertical coverage and better interfacial properties. This study illustrates that 87 nm Au-NPs is the maximum size to attain the improved efficiency, above which the rate of enhancement reduces dramatically.