Vibrational Relaxation Dynamics of a Semiconductor Copper(I) Thiocyanate (CuSCN) Film as a Hole-Transporting Layer.

The semiconductor CuSCN film, which is typically used as the hole-transporting layer (HTL) in solar cell studies, has been investigated by Fourier transform infrared (FTIR) spectroscopy and ultrafast transient infrared (IR) spectroscopy. A sharp peak at 2175 cm-1 corresponding to the CN vibrational stretching mode in CuSCN was observed, and the peak frequency remained unchanged by varying the thickness of the CuSCN thin film. Vibrational relaxation measurements showed that the 0-1 and 1-2 transitions of CN stretching can be observed at 2175 and 2140 cm-1, respectively. The heat-induced absorption and bleaching peaks (2167 and 2175 cm-1) can be clearly seen at a waiting time of 40 ps. The vibrational relaxation of the CN stretching mode determined from the 1-2 transition exhibited a biexponential decay with time constants of 7.4 ± 0.5 (90%) and 158 ± 50 ps (10%). Importantly, the abnormal anisotropy decay of the CN stretching mode in the CuSCN thin film was also observed for the first time. A detailed analysis showed that the distinct anisotropy decay curve could be described using a triexponential decay function, which was explained by three different processes: resonance energy transfer (∼8 ps), a thermalization process (∼40 ps), and molecular rotation (∼150 ps). The time scale of the thermalization process caused by the vibrational relaxation in CuSCN is at a time scale of 40 ps, which is important for us to understand the thermally activated charge-transport property of the CuSCN film employed as the HTL. Further UV pump-IR probe measurement revealed that the carrier scattering and relaxation processes in the CuSCN film are strongly associated with the vibrational excitation and relaxation dynamics of the CN stretching mode. It is expected that the fundamental understanding of the vibrational relaxation dynamics of the CuSCN thin film should provide helpful insight to elucidate its role as the HTL in solar cell studies at the molecular level.