Date on Master's Thesis/Doctoral Dissertation


Document Type

Doctoral Dissertation

Degree Name

Ph. D.


Electrical and Computer Engineering

Committee Chair

Alphenaar, Bruce William

Author's Keywords

Exciton; Plasmon; Organic; Charge transfer; Solar; Polarons


Solar cells; Plasmons (Physics); Exciton theory


Characterization of the optical and electrical properties of organic solar cell materials is of prime importance to organic solar cell design. This thesis describes the use of capacitive photocurrent measurements to study the exciton generation and dissociation mechanisms of organic solar cell materials. The emphasis is on the study of the methanofullerene derivatives (e.g., PCBM) which act as the electron acceptor material. This is because much work has already been done studying electron donating polymers used in organic solar cells (in an effort to enhance their absorbance coefficient), but less information is available on the acceptor material. In the blend films of MDMO-PPV: PCBM, the charge generation rate in PCBM was discovered to be much higher than would be expected from the absorbance cross-section. This observation led to design of a photovoltage bleaching experiment to examine the charge generation mechanism. Here the effect of illumination by a tunable light source on the open circuit photovoltage of a MDMO-PPV: PCBM bulk heterojunction solar cell was measured. Illumination of light at the PCBM ground state singlet exciton causes a sharp decrease in the photovoltage, while illumination at the ground state MDMO-PPV exciton shows no change. A direct pathway of recombination of above gap generated charge carriers was identified. Photovoltage bleaching results suggests that excitation at the PCBM ground singlet state exciton increases the recombination rate of higher energy excitations, either by acting as a recombination center or by forcing higher energy carriers into short lived states that recombine before reaching the contacts. The fact that the photovoltage bleaching correlates with the ground state PCBM singlet exciton suggests that charge dissociation from PCBM preferentially generates long-lived localized states. Capacitive photocurrent measurements were then performed on isolated methanofullerene derivatives, with the polymer donor material absent. Several low energy transitions were resolved in the optical spectroscopy of methanofullerene derivatives. These low energy states lay below the optical energy band-gap of these materials, so that their presence was unexpected. It was determined that the low energy states overlapped with the plasmon state of the highly conducting substrates (Indium Tin Oxide) which were in close proximity with the PCBM. Plasmon states in ITO have been observed previously, but the results presented in this thesis are unique in that this is the first evidence of charge transfer from the plasmon state of ITO to a high electron affinity fullerene derivative. The results show the evidence of charge transfer from PCBM to ITO over a broad wavelength range of 400 - 2400 nm (3 eV - 0.5 eV). Few materials have been observed to have absorbance and charge transfer over such a large range of energies in the infra-red regime. These results open a new direction for development of organic solar cell design with higher power conversion efficiencies.