The
powerful combination of p-polarized multiple-angle incidence
resolution spectroscopy (pMAIRS) and grazing incidence X-ray diffraction
(GIXD) is applied to the structural characterization of zinc tetraphenylporphyrin
(ZnTPP) in vapor-deposited films as a function of the deposition rate.
The deposition rate is revealed to have an impact on the initial film
structure and its conversion by thermal annealing. The pMAIRS spectra
reveal that a fast deposition rate yields a kinetically restricted
amorphous film of ZnTPP having a “face-on orientation”,
which is readily discriminated from another “randomly oriented”
amorphous film generated at a slow deposition rate. In addition, the
GIXD patterns reveal that the film grown at a slow deposition rate
involves a minor component of triclinic crystallites. The different
initial film structure significantly influences the thermal conversion
of ZnTPP films. The randomly oriented amorphous aggregates with the
triclinic crystallite seeds are converted to the thermodynamically
stable phase (monoclinic) via the metastable triclinic phase. The
kinetically restricted structure, on the other hand, is followed by
a simple thermal conversion: the molecules are directly converted
to the monoclinic one rather than the triclinic one.