Polymerization ofpara‐xylylene derivatives (parylene polymerization). IV. Effects of the sublimation rate of di‐p‐xylylene on the morphology and crystallinity of parylene N deposited at different temperatures

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Abstract
The effect of the sublimation rate of di‐p‐xylylene on the crystallinity and morphology of Parylene N deposited on stainless steel was studied as a function of substrate temperature. For a given rate of dimer sublimation, the deposition rate increases with decreasing substrate temperature. Increasing the sublimation rate of the dimer increases the deposition rate 10‐fold, decreases the crystallinity, and shifts the appearance of the hexagonal β structure towards higher substrate temperature for samples synthesized from room temperature (RT) to −60°C. Solution annealing resulting from solvent extraction, and isothermal annealing, increase the crystallinity of the polymers and result in structures containing both α and β polymorphs. The surface topology, as revealed by scanning electron microscopy (SEM), for polymers synthesized from RT to −40°C shows a globular structure, whereas low temperature samples exhibit a rod‐type morphology. For higher sublimation rates of the dimer, SEM micrographs show that oligomeric species start appearing on the polymer films after a period of 4–5 days. Solvent extraction removes the oligomeric crystals, and GPC analysis of the resulting extract indicates that most of the oligomers range in molecular weight from 100 to 900. The cross‐sectional morphology for fractured low temperature samples, however, reveals different morphologies as polymerization proceeds. It is postulated that in the temperature range −50 to −78°C, both surface condensation and surface adsorption of monomer occurs, leading to different morphologies and lower crystallinity. The polymer synthesized at liquid nitrogen temperature shows the presence of voids along with different morphologies. X‐ray diffractograms of polymers synthesized at liquid nitrogen reveal a considerable amount of amorphous phase in the films. Hence, it is inferred that, although the liquid nitrogen polymerization is a solid state polymerization of the crystalline monomer, it does not lead to 100% crystalline material, and the reasons for this are discussed.

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