Impact of gamma-ray irradiation on the electronic structures of PCBM and P3HT organic semiconductor films

Abstract

Gamma-ray irradiation alters the material properties of organic semiconductors, especially the electronic structure. These changes due to ionization can be useful in dosimetry. Although there are some device-based reports, the effect of gamma-ray irradiation on the electronic structure of organic semiconductors is still unclear. In this study, we investigated the electronic structures of representative organic semiconductor films, namely, n-type [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and p-type poly(3-hexylthiophene-2,5-diyl) (P3HT), after gamma-ray irradiation generated by a Cs-137 source. The X-ray and ultraviolet photoelectron spectra of the PCBM and P3HT films were measured for various gamma-ray doses. In both PCBM and P3HT, chemical interaction with atmospheric oxygen, assisted by high-energy photons, led to significant oxidation. However, the degree of oxidation of PCBM was considerably higher than that of P3HT. The oxidation also affects the valence electronic structures. The possible chemical structures of the oxidized PCBM and P3HT are estimated using density functional theory calculations. ？ 2021