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Injection efficiency from evaporated Au contacts on a molecularly doped polymer (MDP) system has been previously observed to evolve from blocking to ohmic over time. In the present article this contact forming phenomenon is analyzed in detail. The initially blocking nature of the Au contact is in contrast with that expected from the relative workfunctions of Au and of the polymer which suggest Au should inject holes efficiently. It is also in apparent contrast to a differently prepared interface of the same materials. The phenomenon is not unique to this interface, having been confirmed also for evaporated Ag and mechanically made liquid Hg contacts on the same MDP. The MDP is a disordered solid state solution of electroactive triarylamine hole transporting TPD molecules in a polycarbonate matrix. The trap-free hole-transport MDP provides a model system for the study of metal/polymer interfaces by enabling the use of a recently developed technique that gives a quantitative measure of contact injection efficiency. The technique combines field-dependent steady state injection current measurements at a contact under test with time-of-flight (TOF) mobility measurements made on the same sample. In the present case, MDP films were prepared with two top vapor-deposited contacts, one of Au (test contact) and one of Al (for TOF), and a bottom carbon-loaded polymer electrode which is known to be ohmic for hole injection. The samples were aged at various temperatures below the glass transition of the MDP (85 °C) and the evolution of current versus field and capacitance versus frequency behaviors are followed in detail over time and analyzed. Control measurements ensure that the evolution of the electrical properties is due to the Au/polymer interface behavior and not the bulk. All evaporated Au contacts eventually achieved ohmic injection. The evaporated Au/MDP interface was also investigated by transmission electron microscopy as a function of time and showed no evidence of Au interdiffusion in the MDP layer, remaining abrupt to within ∼10 Å over the course of the evolution in injection efficiency. Mechanisms related to Au penetration into the MDP are therefore unlikely. Rapid sequence data acquisition enabled the detection of two main processes in the injection evolution. The evolving injection efficiency is very well fit by two exponentials, enabling the characterization of time and temperature dependence of the evolution processes.
Ioannidis et al. (Sat,) studied this question.