How organic switches grafting on TiO₂ modifies the surface potentials: theoretical insights

Hybrid organic switch-inorganic semiconductor systems have important applications in both photo-responsive intelligent surfaces and microfluidic devices. In this context, herein, we performed first-principles calculations to investigate a series of organic switches of trans/cis-azobenzene fluoride and pristine/oxidized trimethoxysilane adsorbed on low-index anatase slabs. The trends in the surface-adsorbate interplay were examined in terms of the electronic structures and potential distributions. Consequently, it was found that the cis-azobenzene fluoride (oxidized trimethoxysilane)-terminated anatase surface attains a lower ionization potential than the trans-azobenzene fluoride (pristine trimethoxysilane)-terminated anatase surface due to its smaller induced (larger intrinsic) dipole moment, whose direction points inwards (outwards) from the substrate, which originates from the electron charge redistribution at the interface (polarity of attached hydroxyl groups). By combining the induced polar interaction analysis and the experimental measurements in the literature, we demonstrate that the ionization potential is an important predictor of the surface wetting properties of adsorbed systems. The anisotropic absorbance spectra of anatase grafted with azobenzene fluoride and trimethoxysilane are also related to the photoisomerization and oxidization process under UV irradiation, respectively.