Microscopic hole-transfer efficiency in organic thin-film transistors studied with charge-modulation spectroscopy

Abstract

While the microscopic transfer properties of carriers are of primary importance for carrier transport of organic semiconductors, the mesoscopic features including the morphologies of grains and the structure of grain boundaries limit the overall carrier transport particularly in polycrystalline organic thin films. Thus the conventional evaluation methods of carrier mobility that rely on macroscopic properties such as $I\text{\ensuremath{-}}V$ curves of devices are not capable to determine carrier transfer probability at the molecular level. Here, we present a method for evaluating the relative strengths of transfer integrals using charge-modulation spectroscopy on thin-film transistors of dinaphtho[$2,3\text{\ensuremath{-}}b$:2\ensuremath{'},3\ensuremath{'}-$f$]thieno[$3,2\text{\ensuremath{-}}b$]thiophene (DNTT) and its alkylated derivatives (${\mathrm{C}}_{n}$-DNTT, $n=8$, 10, and 12). The band edges of absorption spectra of holes at around 1.9 eV show bathochromic shifts with increasing length of alkyl chains introduced at both ends of a DNTT chromophore. Applying a two-dimensional model with Holstein-type Hamiltonians to electronic transitions of holes, we have been able to simulate the features of the absorption band edges observed. The simulations indicate that the bathochromic shifts are due to an increase in the transfer integrals of holes with increasing length of alkyl chains. Thus this analysis confirmed that the subtle changes in the mutual orientations between adjacent DNTT chromophores induced by alkyl chains enhance the microscopic hole transfer rate. Although this fastener effect has been suggested by hole mobility measurements by $I\text{\ensuremath{-}}V$ curves, the spectral analysis in this study gives clear evidence of this effect at the molecular level.