Comparing the growth of a molecular semiconductor on amorphous and semi-crystalline polycarbonate substrates

Polymeric substrates are of importance in plastic electronics. However, polymeric surfaces can exhibit different morphologies depending on whether they are amorphous or semi-crystalline. This work focuses on the impact of the surface structure of bisphenol A polycarbonate substrates on the nucleation and growth of a p-type semi-conductor, namely zinc phthalocyanine (ZnPc). ZnPc films were deposited under high vacuum at different substrate temperatures on oriented semi-crystalline as well as amorphous substrates of PC. The oriented substrates of PC were prepared by a method combining mechanical rubbing and solvent induced crystallization: the substrates show a periodic and regular alternation of oriented crystalline lamellae. Grazing incidence X-ray diffraction shows that the crystalline lamellae of PC have a preferential (a, c) contact plane. Moreover, the substrates show a bilayer structure made of a 60 nm-thick semi-crystalline overlayer atop an amorphous underlayer. UV–vis spectroscopy shows that the polymorphism of the ZnPc films is not modified by the surface structure of the PC substrate (amorphous versus semi-crystalline). However, the statistical analysis of domain size and density versus substrate temperature Ts evidences different apparent activation energies of the growth mechanism. High Resolution Transmission Electron Microscopy suggests that twinning along a (2 −1 0) plane accounts for the bifurcations of the in-plane b-axis direction of the ZnPc nanocrystals. On oriented substrates of PC, such bifurcations are partly suppressed by the nanocorrugation of the surface, resulting in larger apparent domain sizes and unidirectional in-plane orientation.

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► Highly oriented zinc phthalocyanine films are grown on semicrystalline polycarbonate.
► ZnPc nanocrystals grow larger on semicrystalline versus amorphous PC substrates.
► Twinning defects explain the bifurcation of stacking direction in ZnPc nanocrystals.