Electronic Thesis and Dissertation Repository


Doctor of Philosophy




Oleg Semenikhin


The semiconductor and photovoltaic properties of carbon nitride (CNx) thin films prepared using a reactive magnetron sputtering technique were investigated both individually and as composites with the organic conjugated polymers polybithiophene (PBT) and poly(3-hextlthiophene) (P3HT). At low nitrogen content, the film structure was dominated by graphitic sp2 percolation networks, whereas at higher nitrogen contents CNx films started to demonstrate semiconductor properties, as evidenced by the occurrence of photoconductivity and the development of a space charge region. When CNx was deposited onto a PBT substrate, it was found to function as an acceptor material improving the photocurrent generation both in solution and in solid state photovoltaic devices, with the external quantum efficiencies reaching 1% at high nitrogen contents. The occurrence of the donor–acceptor charge transfer was further evidenced by suppression of the n-doping of the PBT polymer by CNx. Nanoscale atomic force microscopy (AFM) and current-sensing AFM data suggested that CNx may form a bulk heterojunction with PBT. Thermal annealing of nitrogen rich CNx films led to n-type semiconductor materials consisting of a graphitic carbon nitride network as determined using X-ray photoelectron spectroscopy, and these materials exhibited photovoltaic properties. Intensity modulated photocurrent (IMPS) and photovoltage (IMVS) spectroscopies were used to study the mechanism of photoprocesses in P3HT:PCBM ([6,6]-phenyl C61 butyric acid methyl ester ) bulk heterojunction organic solar cells at various light intensities. The use of the frequency domain techniques allowed us to separate the bulk and interfacial processes and gain valuable insight into the mechanism of losses in these devices. The results provide direct evidence that interfacial nongeminate recombination is one of the dominant loss and aging mechanisms in bulk heterojunction organic solar cells. The trapping of photoexcited holes in the P3HT phase was found to contribute to the increased recombination rate. It was determined that interfacial recombination occurs at the P3HT/PCBM interface and that higher PCBM contents help to improve charge carrier extraction. The results suggest that promising ways of improving the efficiency of bulk heterojunction solar cells may be reducing the charge trapping both at and near the P3HT:PCBM interface, as well as improving the efficiency of charge extraction at the contacts.