Orientational and Crystalline Order of Copper–Phthalocyanine Films on Gold: the Role of Substrate Roughness and Cleanliness
2019-10-10T14:03:50Z (GMT) by
Although metal phthalocyanines are widely used in optoelectronic devices, e.g., as hole-transport and electron-blocking layers, or as UV-stable dyes, their multilayer growth on metal substrates has surprisingly not been studied very systematically. Even for CuPc, one of the most widely studied representatives of phthalocyanines, contradictory structures are reported for films grown on gold, a common electrode material, suggesting that the influence of actual substrate surface properties on film growth has not been sufficiently considered. In this study, we analyze the growth of CuPc films on gold substrates for thicknesses ranging from the initial seed layer to thick multilayers (50 nm) by combining near-edge X-ray absorption spectroscopy with atomic force microscopy and X-ray diffraction. To study the influence of surface roughness, we compare the formation of CuPc films on well-ordered Au(111) and sputter-deposited polycrystalline gold substrates and also investigate the influence of surface contamination by exposing these gold surfaces to air before film growth. While on clean gold substrates, CuPc molecules exclusively adopt a recumbent orientation and form (112̅)-oriented films, they also grow in an upright orientation on contaminated gold surfaces. On Au(111), this leads to the coexistence of (112̅)- and (100)-oriented regions, whereas only (100)-oriented films are formed on contaminated polycrystalline gold. Remarkably, the (112̅)-oriented films consist of extended but isolated crystalline islands, resulting in large overall roughness, whereas the (100)-oriented films consist of rather small domains but have significantly lower film roughness.