Image-force effects on energy level alignment at electron transport material/cathode interfaces

Electron transport materials (ETMs) are widely used as interlayers to lower the cathode electrode work function in organic solar cells and organic light-emitting diodes, for example. The usual interpretation for their operating principle is a chemical interaction between the ETM and the electrode, inducing partial or integer charge transfer or collectively an intrinsic dipole moment caused by preferential molecular orientation. Herein, we systematically explore the commonly used ETM bathophenanthroline (BPhen) deposited on a series of conducting substrates. The energetics at the BPhen interface follows the typical integer charge transfer (ICT) model with an extra displacement of the vacuum level by up to -1.4 eV. The extra displacement is ascribed to the "double dipole step" formed by the positive and negative charged species and their induced image charges when they are close to the surface of substrates. After n-type doping the displacement is further increased to -1.8 eV, yielding a larger work function modification than obtained using typical electrolytes and zwitterions as cathode interlayer. Funding Agencies|Knut and Alice Wallenberg Foundation project "Tail of the Sun; Swedish Research CouncilSwedish Research Council [2016-05498]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [SE13-0060]; Ministry of Science and TechnologyMinistry of Education, Culture, Sports, Science and Technology, Japan (MEXT)Ministry of Science and Technology, Government of India [2016YFA0200700]; NSFCNational Natural Science Foundation of China [21504066, 21534003]; Swedish Energy AgencySwedish Energy Agency [45411-1]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO Mat LiU) [2009 00971]