Prevention and characterization of thin film defects induced by contaminant aggregates in initiated chemical vapor deposition

As initiated Chemical Vapor Deposition (iCVD) finds increasing application in precision industries like electronics and optics, defect prevention will become critical. While studies of non-ideal morphology exist in the iCVD literature, no studies investigate the role of defects. To address this knowledge gap, we show that the buildup of short-chain polymers or oligomers during normal operation of an iCVD reactor can lead to defects that compromise film integrity. We used atomic force microscopy to show that oligomer aggregates selectively prevented film growth, causing these hole-like defects. X-ray diffraction and optical microscopy demonstrated the crystallinity of the aggregates, pointing to a flat-on lamellar or mono-lamellar structure. To understand the origin of the aggregates, spectroscopic ellipsometry showed that samples exposed to the reactor consistently accrued low-volatility contaminants. X-ray photoelectron spectroscopy revealed material derived from polymerization in the contamination, while scanning electron microscopy showed the presence of defect-causing aggregates. We directly linked oligomeric/polymeric contamination with defect formation by showing an increased defect rate when a contaminant polymer was heated alongside the sample. Most importantly, we showed that starting a deposition at a high sample temperature (e.g., 50 °C) before reducing it to the desired setpoint (e.g., 9 °C) unilaterally prevented defects, providing a simple method to prevent defects with minimal impact on operations.