Kelvin probe study of band bending at organic semiconductor/metal interfaces: examination of Fermi level alignment

Band bending is a fundamental issue for discussing organic devices. Band bending with Fermi level alignment between semiconductors and metals are often assumed, although the validity of this scheme in the case of organic semiconductors has been not yet established. In this paper, our recent efforts to examine band bending in organic semiconductors using Kelvin probe method (KPM) are reported. After discussing the applicability of KPM to organic thick film – metal substrate system, the results for C60, TPD, and Alq3 are shown to discuss band bending of the films without intentional doping in ultrahigh vacuum condition. Gradual band bending was observed for C60/metal interfaces although the width of the space charge layer is in the order of 100 nm. In contrast, flat band feature was observed for TPD/metal interfaces probably because of its high purity. These results demonstrate that the frame work of band bending used in inorganic semiconductor interfaces is still valid for organic semiconductors although much thicker films are often necessary to achieve bulk Fermi level alignment. For Alq3/metal interfaces formed in dark condition, we found a new type of band bending where the energy levels change as a linear function of the distance from the interface. The observed location of the vacuum level was far below the Fermi level of the metal substrates, clearly indicating that Fermi level varies place by place in the system. Such electronically non-equilibrium state was quite stable for the order of years. The concept of Fermi level alignment is also discussed in relation to the observed energy diagrams. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)