Polymer/metal interfaces and the performance of polymer light-emitting diodes

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Abstract
Conjugated polymers are often treated as semiconductors with low doping concentrations. Unlike the traditional semiconductors which have a high density of surface states (mainly due to the dangling bonds), the nature of the metal/polymer interface, including barrier height and charge injection efficiency, is quite sensitive to the work function of the contact metal. In this article, we present evidence to show that the pinning of the surface Fermi level effect commonly observed at the silicon/metal interface can also be observed at the metal/polymer interface. It is achieved by controlling the doping level at the metal/polymer [poly(2-methoxy-5(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) or MEH-PPV] interface. ITO/MEH-PPV/Al devices doped with 2 Å of calcium on the cathode side of the interfacial layer have the same device performance as the ITO/MEH-PPV/Ca devices. The heavily n-doped region pins the surface energy level, hence the polymer interface at the cathode side is no longer sensitive to the work function of the overcoated metal. It is believed that either the midgap bipolaron energy states created by the dopants or the sharp band bending at the interface is responsible for facilitating the electron injection. On the other hand, a p-doped region at the anode side, obtained by using a thin layer of an acid at the interface, pins the surface energy level and makes the contact insensitive to the work function of the anode. Therefore, an efficient polymer light-emitting diode with the p-i-n structure has been demonstrated without the matching of the work function of the metal electrodes.