Highly oriented films of titanyl phthalocyanine (TiOPc) were obtained by high-vacuum
sublimation onto an oriented poly(tetrafluoroethylene) (PTFE) substrate. The dependence
of the structure and morphology on deposition parameters (substrate temperature T
s,
deposition time t, and deposition rate τ) was followed by X-ray diffraction, transmission
electron microscopy (TEM), and atomic force microscopy (AFM) to uncover the origin of the
oriented growth process. At T
s = 100 °C, an original growth mechanism was observed
whereby α-TiOPc microcrystallites were formed by the static coalescence and reorganization
of small amorphous aggregates in close contact. Nucleation of α-TiOPc is initiated at the
PTFE macrosteps from which oriented crystallization propagates, leading to uniform α-TiOPc
films with a twinned texture and a dense (0 1 0) contact plane. The molecules are in an
edge-on orientation, with their molecular plane oriented parallel to the PTFE chains. At
the mesoscale, the nucleation of crystalline α-TiOPc involves the alignment and oriented
coalescence of amorphous prenucleation aggregates along the PTFE macrosteps, i.e., a
graphoepitaxial process. At the molecular scale, it is proposed that the TiOPc orientation
and the preferential nucleation of the α polymorph are enforced by the topography and
structure of the PTFE macrosteps in conjunction with the requirement for a minimal
nucleation free energy. The optical absorption of the films in the near infrared is found to
be strongly correlated with the structural and morphological modifications in the films. The
oriented character of the α-TiOPc films results in a strong polarization of the 850-nm band
perpendicular to the PTFE chain axis direction.