A Solvent‐Free Solution: Vacuum‐Deposited Organic Monolayers Modify Work Functions of Noble Metal Electrodes

The energy level alignment between organic semiconductors (OSCs) and the respective (metal) electrodes in organic electronic devices is of key importance for efficient charge carrier injection. For many years, researchers have attempted to control this energy level alignment by means of functional self‐assembled monolayers or the insertion of thin injection layers (made, e.g., of doped OCSs or pure dopants). The present work demonstrates an alternative to these approaches, namely the use of phthalocyanine monolayers as contact primers, which are deposited onto noble metal electrodes by means of vacuum deposition. It is shown that polar as well as non‐polar phthalocyanines modify the work functions of clean Au(111) and Ag(111) surfaces as a function of their coverage and thus enable quantitative control of the metal work functions. This behavior is successfully replicated for the respective polycrystalline metal surfaces and it is found that full monolayers can even withstand air exposure when protected by sacrificial multilayers, which are afterward removed by thermal desorption. In this study, polar and non‐polar phthalocyanines are tested as vacuum‐deposited primer layers for contact engineering in organic electronics. The coverage dependence of noble metal work functions is examined for single crystal model surfaces and more device‐relevant polycrystalline substrates and several simple and user‐friendly methods for implementing such contact primers into an existing device fabrication process are suggested.