Plasmon-enhanced optical absorption and photocurrent in organic bulk heterojunction photovoltaic devices using self-assembled layer of silver nanoparticles

Improved optical absorption and photocurrent for polythiophene–fullerene bulk heterojunction photovoltaic devices is demonstrated using a unique self-assembled monolayer of Ag nanoparticles formed from a colloidal solution. With the presence of suitable nanoparticle organic capping groups that inhibit its propensity to agglomerate, the particle-to-particle spacing can be tailored. Transmission electron microscopy reveals the self-assembled Ag nanospheres are highly uniform with an average diameter of ∼4 nm and controllable particle-to-particle spacing. The localized surface plasmon resonance peak is ∼465 nm with a narrow full width at half maximum (95 nm). In the spectral range of 350–650 nm, where the organic bulk heterojunction photoactive film absorbs, an enhanced optical absorption is observed due to the increased electric field in the photoactive layer by excited localized surface plasmons within the Ag nanospheres. Under the short-circuit condition, the induced photo-current efficiency (IPCE) measurement demonstrates that the maximum IPCE increased to ∼51.6% at 500 nm for the experimental devices with the self-assembled layer of Ag nanoparticles, while the IPCE of the reference devices without the plasmon-active Ag nanoparticles is ∼45.7% at 480 nm. For the experimental devices under air mass 1.5 global filtered illuminations with incident intensity of 100 mW/cm2, the increased short-circuit current density is observed due to the enhancement of the photogeneration of excitons near the plasmon resonance of the Ag nanoparticles.