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The effects of the electric-field-assisted annealing on the bulkheterojunction nano-morphology in the P3HT/PCBM active layer of the organicphotovoltaic cells (OPVCs) are presented here. It was widely accepted that theelectric-field-assisted annealing will facilitate the P3HT, the polar polymer,to be better crystalline to enhance the charge mobility, hence the improvementof the OPVC performance. The influences on the nano-morphology of the electrondonor and accepter domains are not well understood. Here, using thecross-sectional scanning tunneling microscopy and spectroscopy (XSTM/S), theelectric-field-assisted annealing treatment is found to influence the moleculardomains to be elongated with the orientation near the direction of the externalelectric field. The elongation of the molecular domains is believed tofacilitate the domain percolation, which causes higher charge mobility, hencethe higher short-circuit current density (Jsc). On the other hand, it was alsoobserved that the electronic properties of the P3HT-rich and PCBM-rich domainsin the electric-field-assisted annealed samples showed smaller energy band gapsand smaller molecular orbital offset between the two domains, which is arguedto decrease the open circuit voltage (Voc) and negatively impact the OPVCperformance. Based on the X-ray diffraction (XRD) and small angle X-rayscattering (SAXS) results, the altered electronic properties are argued to bedue to the molecular intermixing induced doping effects. These results pointout competing factors affecting the OPVC performance with theelectric-field-assisted annealing treatment.

Elongated Nano Domains and Molecular Intermixing induced Doping in Organic Photovoltaic Active Layers with Electric Field Treatment