Interface and charge transport studies in organic solar cells based on P3HT:PCBM bulk heterojunctions

Rujisamphan, Nopporn
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University of Delaware
Interfaces and charge transport in organic solar cells based on P3HT:PCBM bulk heterojunctions (BHJ) were studied. State-of-the-art TEM sample preparation techniques, including in-situ lift-out, were used with a dual focused ion beam (FIB) system on a typical device (ITO/PEDOT:PSS/P3HT:PCBM/Al). Through bright field (BF) TEM micrographs a mixed layer between the Al electrode and the organic active layer (P3HT:PCBM) was clearly observed in both as-fabricated and annealed devices. The effect of Al contact resistance before and after annealing was studied using the vertical transmission line model (TLM). It was found that by annealing after Al evaporation, the contact resistivity decreased by 38%. Energy filtered transmission electron microscopy (EFTEM) clearly revealed a nanoscopic phase separation. From the EFTEM images, the average length and the diameter of P3HT fibrils were found to be approximately 70 nm and 15 nm, respectively. Combining the EFTEM, selected area electron diffraction (SAED) patterns and X-ray diffraction (XRD) results, the number and spacing of the ordered polymer chains in P3HT fibrils were calculated. There were about 18 repeating units of P3HT perpendicular to the fibril, about 184 layers of pi-pi* stacking along the fibril and about 9 layers of interchain stacking within the fibril. Accompanied by cross-section samples prepared by the FIB technique, the vertical morphology of each phase was analyzed. By collecting 30 eV energy loss images, the phase separation in the blend of P3HT:PCBM was distinguishable. A higher P3HT concentration was observed at the top of the cell. The temperature dependent charge separation and charge transport were studied using modulated surface photovoltage spectroscopy (SPV) on layers of P3HT, PCBM, and the blend. The unchanged character of the SPV spectra on the P3HT provides evidence that the mechanisms of charge separation, recombination and charge transport does not change qualitatively after cooling. It was important to point out that the SPV onset of the blend (P3HT:PCBM) occurred at a photon energy of about 1.0 eV, which was not in the range of reported optical band gap of either P3HT or PCBM. These SPV signals were assigned to charge separation from charge transfer (CT) states laying within the band gap of P3HT.