Organic solar cells based on highly self-organizing semiconducting polymers

In this thesis I have studied organic solar cells (photovoltaic devices) based on a highly self-organizing polymer, regioregular poly(3-hexyIthiophene) (P3HT), because of its particular crystallization tendency leading to high charge carrier mobilities, good light-harvesting in red parts, and suitable energy band structure for an electron-donor. Prior to organic solar cell study, the pristine P3HT films have been investigated to understand their optical/electrical property and nanocrystal structure changes upon thermal annealing. As an electron-acceptor for organic solar cells, two candidates were employed: One is polymer [poly(poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT)), another is big small molecule [[6,6]-phenyl Cgi-butyric acid methyl ester (PCBM)]. The kinds of blends used for organic solar cell fabrication were P3HT:F8BT, P3HT:PCBM, and P3HT:PCBM:F8BT. Organic solar cells were fabricated by spin-coating these blend films onto transparent conductive oxide coated substrates followed by depositing metal electrodes (sometimes inserting LiF). For better understanding of device performance changes, blend films have been examined with optical absorption, photoluminescence including time-resloved system, normal reflection mode x-ray diffraction, grazing incidence x-ray diffraction (Synchrotron), atomic force microscopy, scanning electron microscopy, high resolution transmission electron microscopy with field emission gun, transient absorption spectroscopy, and time-of-flight mobility measurement. As a result, P3HT:F8BT solar cells (maximum external quantum efficiency=~3%) showed poorer efficiency than P3HT:PCBM solar cells (maximum external quantum efficiency=~73%), though both blends have P3HT components, which is attributed to the low electron mobility of F8BT compared to PCBM. The power conversion efficiency of P3HT:PCBM solar cells has reached 4.4-5.5% at 85~8.5mW/cm^ (air mass 1.5 simulated solar illumination), which is ascribed mainly to the formation of vertical phase segregation upon thermal annealing leading to pseudo layered p-n junction. This layered structure might reduce the charge recombination between P3HT positive polaron (radical cation) and PCBM negative polaron (radical anion), a parameter that has been quantitatively analysed using a new model proposed in this work