Layer-by-Layer Self-Assembled Graphene Multilayers as Pt-Free Alternative Counter Electrodes in Dye-Sensitized Solar Cells

Low cost, charged, and large scale graphene multilayers fabricated from nitrogen-doped reduced graphene oxide N-rGO(+), nitrogen and sulfur codoped reduced graphene oxide NS-rGO(+), and undoped reduced graphene oxide rGO(-) were applied as alternative counter electrodes in dye-sensitized solar cells (DSSCs). The neat rGO-based counter electrodes were developed via two types of layer-by-layer (LBL) self-assembly (SA) methods: spin coating and spray coating methods. In the spin coating method, two sets of multilayer films were fabricated on poly(diallyldimethylammonium chloride) (PDDA)-coated fluorine-doped tin oxide (FTO) substrates using GO(-) combined with N-GO(+) followed by annealing and denoted as [rGO(-)/N-rGO(+)]_n or with NS-GO(+) and denoted as [rGO(-)/NS-rGO(+)]_n for counter electrodes in DSSCs. The DSSCs employing new types of counter electrodes exhibited ∼7.0% and ∼6.2% power conversion efficiency (PCE) based on ten bilayers of [rGO(-)/N-rGO(+)]₁₀ and [rGO(-)/NS-rGO(+)]₁₀, respectively. The DSSCs equipped with a blend of one bilayer of [rGO(-):N-rGO(+)] and [rGO(-):NS-rGO(+)] on PDDA-coated FTO substrates were prepared from a spray coating and showed ∼6.4% and ∼5.6% PCE, respectively. Thus, it was demonstrated that a combination of undoped, nitrogen-doped, and nitrogen and sulfur codoped reduced graphene oxides can be considered as potentially powerful Pt-free electrocatalysts and alternative electrodes in conventional photovoltaic devices.