Spectra of one-dimensional excitons in polysilanes with various backbone conformations

Abstract

Linear and nonlinear optical spectra (one-photon and two-photon absorption, photoluminescence, and electroabsorption spectra) have been investigated for solid thin films of polysilanes with a variety of conformations, such as trans-planar, alternating trans-gauche (TGTG' type), 7/3 helical, and disordered backbone structures. Optical spectra have revealed features of one-dimensional exciton states characteristic of the respective conformations. In particular, the lowest allowed and second parity-forbidden (or two-photon allowed) transitions can be assigned to the ground ${(}^{1}$${\mathit{B}}_{1\mathit{u}}$) and first excited ${(}^{1}$${\mathit{A}}_{\mathit{g}}$) states of one-dimensional Wannier-type exciton, respectively. Furthermore, the higher excited exciton states and subsequent band-to-band transitions show up in the electroabsorption spectra for polysilanes with various conformations of the Si backbones. Quantitative analysis based on a microscopic theory for the one-dimensional excitons is also presented.