The energy level alignment of the ferrocene-EGaIn interface studied with photoelectron spectroscopy

The energy level alignment after the formation of a molecular tunnel junction is often poorly understood because spectroscopy inside junctions is not possible, which hampers the rational design of functional molecular junctions and complicates the interpretation of the data generated by molecular junctions. In molecular junction platforms where the top electrode-molecule interaction is weak; one may argue that the energy level alignment can be deduced from measurements with the molecules supported by the bottom electrode (sometimes referred to as “half junctions”). This approach, however, still relies on a series of assumptions, which are challenging to address experimentally due to difficulties in studying the molecule-top electrode interaction. Herein, we describe top electrode-molecule junctions with a liquid metal alloy top electrode of EGaIn (which stands for eutectic alloy of Ga and In) interacting with well-characterised ferrocene (Fc) moieties. We deposited a ferrocene derivative on films of EGaIn, coated with its native GaO_xlayer, and studied the energy level alignment with photoelectron spectroscopy. Our results reveal that the electronic interaction between the Fc and GaO_x/EGaIn is very weak, resembling physisorption. Therefore, investigations of “half junctions” for this system can provide valuable information regarding the energy level alignment of complete EGaIn junctions. Our results help to improve our understanding of the energy landscape in weakly coupled molecular junctions and aid to the rational design of molecular electronic devices.