para-Sexiphenyl thin film growth on Cu(1 1 0) and Cu(1 1 0)–(2 × 1)O surfaces

We present a reflectance difference spectroscopy (RDS) study of para-sexiphenyl (p-6P) thin film growth on Cu(1 1 0) and Cu(1 1 0)–(2 × 1)O substrates. The RDS spectra show pronounced anisotropies for p-6P films formed on both substrates at room temperature, demonstrating that the molecules are uniaxially aligned within the films. Based on the RD spectra and the evolution of the optical transitions with p-6P coverage the growth mode on both substrates could be identified. From the dominating RDS feature, assigned to the lowest energy HOMO–LUMO transition, the orientation of the molecular chain can be determined. On Cu(1 1 0), the p-6P molecular chains align in the [ 1 ¯ 1 0 ] direction, i.e., along the Cu atomic rows, whereas on the Cu(1 1 0)–(2 × 1)O surface, the molecules are oriented in the orthogonal [0 0 1] direction, i.e., along the “added” Cu–O rows of the Cu(1 1 0)–(2 × 1)O surface. The energetic position and line shape of the main RDS feature differs for the two substrates and varies with p-6P coverage. This fine structure is discussed in terms of different molecular conformations, adlayer structure and vibronic replicas.