Hierarchical self-assembly of all-organic photovoltaic devices

Photovoltaic devices built by a hierarchical self-assembly process using hydrogen-bonding terminated self-assembled monolayers (SAMs) on gold and the combination of a hydrogen-bonding barbituric acid appended fullerene and a complementary melamine terminated π-conjugated thiophene-based oligomer are presented. The incorporation of these electron donor (oligomer) and electron acceptor (methanofullerene) assemblies into simple photovoltaic (PV) devices as thin films leads to a 2.5 fold-enhancement in photocurrent compared to analogous systems comprising non-hydrogen-bonding C₆₀-oligomer systems, which is ascribed to higher molecular-level ordering. The modification of the gold electrode surface with self-assembled monolayers bearing hydrogen-bonding molecular recognition endgroups was seen to further enhance the PV response of the corresponding functional supramolecular device. This superposition of two types of self-assembly facilitates the generation of binary supramolecular fullerene-containing architectures. Importantly, all functional materials are accessible in a direct fashion.