Jiakai Liu

May 2013
Computational Materials Design of Optical Bandgaps for Bulk Heterojunction Solar Cells
Committee Members: Advisor: Xi Lin, MSE/ME; David Campbell, CAS Physics; Linda Doerrer, MSE/CAS Chemistry; Ramesh Jasti, MSE/CAS Chemistry

Abstract: Fundamental understanding of the structure-property relationship of pi-conjugated polymers is critical to predictive materials designs of bulk heterojunction solar cells. In this thesis, the adapted Su-Schrieffer-Heeger Hamiltonian is implemented as the computational tool to systematically explore the opto-electronic properties of nearly 250 different kinds of pi-conjugated systems. New physical insights on the structure-property relationship are extracted and transformed into practical guiding rules in optical bandgap designs.

For the most power efficient donor-acceptor copolymer structures, we find that the energy variation of frontier orbitals, in particular the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO), can be controlled either independently or collectively, depending on their specific donor or acceptor structures. In particular, we find that having five-membered conjugated carbon rings in the acceptor units is essential to break the electron-hole charge conjugation symmetry, so that the LUMO levels of the copolymer can be reduced dramatically while holding the HOMO energy levels in the donor units constant. On the other hand, by incorporating heteroatoms

into the donors units, we can vary the HOMO levels of the copolymers independently. Predicted optical bandgaps of a total of 780 types of these copolymers constructed by using 39 different types of donor and acceptor units are tabulated in this thesis. In addition, the effects of introducing various side groups(-R, -O, -CO, -COO, and thiophene) on the primitive donor and acceptor structures are investigated and their results are discussed in details. Finally, unexpected localized states are found, for the first time, in our calculations for a few special co-polymer structures. These localized states, with electrons localized on one end of the copolymer chain and holes on the other end, contain large dipole moments and therefore may be treated as a new design dimension when these copolymers are placed in polar and non-polar solvent environments.