Interface electronic structure between organic semiconductor film and electrode metal probed by photoelectron yield spectroscopy

We present an investigation of the interface between organic semiconductor films and metal substrates (organic/metal interface) using photoelectron yield spectroscopy (PYS) as the probing technique. PYS studies were conducted on the pentacene/Au, copper phthalocyanine (CuPc)/Au, and perfluorinated zinc phthalocyanine (F₁₆ZnPc)/Au, and the results were compared with literature results obtained using conventional ultraviolet photoemission spectroscopy (UPS). PYS is advantageous for probing the electronic structure of the organic/metal interface because of the relatively long mean free path of photoexcited electrons with very low kinetic energy in PYS, which enables the detection of the photoelectrons from the metal substrate buried deep in the organic film. We demonstrate herein that the use of PYS reduces the significance of the final state effect of the electronic density surrounding the photohole at the organic molecule generated after the photoemission; this effect is known as the electric polarization effect. Although this effect has a significant influence on the results obtained using conventional UPS, the reduced influence of the final state effect in PYS makes it possible to construct an energy level diagram at the organic/metal interface with greater accuracy than can be achieved with UPS. In addition, a novel mechanism of the photoelectron detection for PYS enables us to apply PYS to very thick organic films, and therefore, PYS provides a reliable value of ionization energy for organic films without the influence of the substrate.Because the interface electronic structure has a significant influence on the carrier injection properties of organic devices, the increased reliability of the information obtained by PYS will render it very useful for the improvement of device performance as well for understanding their operation principles.