Binary Self-Assembly of Conjugated Block Copolymers and Quantum Dots at the Air-Liquid Interface into Ordered Functional Nanoarrays

Controlling the nanoscale morphology of conducting polymer/nanoparticle hybrid films is a highly desired but challenging task. Here, we report that such functional hybrid films with unprecedented structural order can be formed through the self-assembly of conjugated block copolymers and CdSe quantum dots at the air-water interface. The one-step assembly of quantum dots and block copolymers composed of polythiophene and polyethylene glycol (P3HT-b-PEG) at the fluidic interface generated a highly ordered assembly structure of P3HT nanowires and one-dimensional quantum dot arrays. Structure analyses revealed a unique self-assembly behavior and size dependency, which are distinct from the conventional self-assembly of coil-type polymers on solid substrates. Interestingly, hydrophobic quantum dots reside at the interface between P3HT and PEG domains without disrupting the P3HT packing structure, which is advantageous for the optoelectronic properties. Furthermore, large particles bridge the P3HT nanowires at both ends, while small particles decorate each P3HT/PEG interfaces, thus forming tight p-n junctions for a broad size range of nanoparticles. The nanoparticle-incorporated hybrid films showed more than an order of magnitude higher photocurrent and light sensitivity compared to polymer-only films, consistent with the assembly structure with close contact between the organic and inorganic semiconductors.