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The chemical modification of electrodes with organic materials is a commonapproach to tune the electronic and electrostatic landscape between interlayersin optoelectronic devices, thus facilitating charge injection at theelectrode/semiconductor interfaces and improving their performance. The use ofphotochromic molecules for the surface modification allows dynamic control ofthe electronic and electrostatic properties of the electrode and therebyenables additional functionalities in such devices. Here, we show that theelectronic properties of a transparent indium tin oxide (ITO) electrode arereversibly and dynamically modified by depositing organic photochromic switches(diarylethenes) in the form of self-assembled monolayers (SAMs). By combining arange of surface characterization and density functional theory calculations,we present a detailed picture of the SAM binding onto ITO, the packing densityof molecules, their orientation, as well as the work function modification ofthe ITO surface due to the SAM deposition. Upon illumination with ultravioletand green light, we observe a reversible shift of the frontier occupied levelsby 0.7 eV, and concomitantly a reversible work function change of ca. 60 meV.Our results prove the viability of dynamic switching of the electronicproperties of the electrode with external light stimuli, which could be used tofabricate ITO-based photo-switchable optoelectronic devices.

Dynamically switching the surface electronic and electrostatic properties of indium tin oxide electrodes with photochromic monolayers