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Polymorphism in Phthalocyanine Thin Films: Mechanism of the r f β Transition
Polymorphism in Phthalocyanine Thin Films: Mechanism of the r f β Transition
Two different polymorphic forms of free base phthalocyanine films have been grown on glass substrates by
ultrahigh vacuum organic molecular beam deposition. Postgrowth annealing of films grown at room temperature
leads to transformation from the R to the β1 phase. The effects of annealing lead to a number of transition
states whose morphological, structural, and spectroscopic properties can be identified using atomic force and
optical interference microscopy, X-ray diffraction, and Raman and electronic absorption spectroscopy. Detailed
morphological studies indicate that the transition occurs via a discrete number of nucleations and is preceded
by an elongation of the R crystallites. Quantitative analysis of the crystallites and domain size shows that the
individual β1 crystals grow but are confined to domains of similar orientation. The film thickness plays a
critical role and three regimes have been identified. The R f β1 transformation is only complete for films
thicker than ∼940 Å, and thick films lead to a higher degree of orientation and larger domains.
while the individual crystallites continue to grow until they (University of Liège, Belgium) for the X-ray diffraction
finally merge. measurements. S.H. thanks the Department of Chemistry,
The thickness of the film plays an important role and three Imperial College, for a postgraduate teaching assistantship.
regimes are observed for films of different thickness. The S.M.B. is grateful to the Engineering and Physical Sciences
extreme case is for thin films, i.e., less than 560 Å. The R f Research Council (EPSRC), U.K., for the provision of a Ph.D.
β1 transformation is inhibited since the R phase is supposed to studentship. This work was supported by the EPSRC, U.K.
be the most stable for reduced thickness, and sublimation occurs
without any transformation. For films between 560 and 940 Å References and Notes
only partial transformation of the film occurs, indicating that
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