Electron transport properties in fluorinated copper-phthalocyanine films: importance of vibrational reorganization energy and molecular microstructure.

Electron transport (ET) properties of a series of fluorinated copper-phthalocyanine (F(16)CuPc) thin films, which were deposited at different substrate temperatures (T(sub)) ranging from 30 to 150 degrees C, have been investigated by quantum mechanical calculations of the reorganization energy (lambda(reorg)), X-ray diffraction (XRD), atomic force microscopy (AFM), and microRaman spectroscopy. Density functional theory calculations were used to predict the vibrational frequencies, normal mode displacement vectors, and electron-vibrational lambda(reorg) for the F(16)CuPc molecule. The electron mobilities (mu(e)) of F(16)CuPc thin films are strongly dependent on the T(sub), and the value of mu(e) increases with increasing T(sub) from 30 to 120 degrees C, at which point it reaches its maximum value. The importance of electron-vibrational coupling and molecular microstructures for ET properties in F(16)CuPc thin films are discussed on the basis of theoretical vibrational lambda(reorg) calculations and experimental observations of resonance Raman spectra. We observed a good correlation between mu(e) and the full-width-at-half-maximum of the vibrational bands, which greatly contributed to lambda(reorg) and/or which reflects the molecular microstructural quality of the active channel. In contrast, the crystal size analysis by XRD and surface grain morphology by AFM did not reveal a clear correlation with the ET behaviours for these different F(16)CuPc thin films. Therefore, we suggest that for organic films with weak intermolecular interactions, such as F(16)CuPc, optimized microscopic molecular-scale parameters are highly important for efficient long-range charge transport in the macroscopic devices.