Date of Award

9-2009

Degree Name

MS in Engineering - Materials Engineering

Department

Materials Engineering

Advisor

Richard Savage

Abstract

Polymeric materials have provided pathways to products that could not be manufactured otherwise. A new technology which merges the benefits of ceramics into these polymer products has created materials ideally suited to many different industries, like food packaging. Nano Scale Surface Systems, Inc. (NS3), a company which coats polymers with ceramic oxides like SiO2 through a process known as plasma enhanced chemical vapor deposition (PECVD), was interested in the feasibility of an in line measurement system for monitoring the deposited films on various polymer products. This project examined two different coated polymer products, polyethylene terephthalate (PET) beverage containers and biaxially oriented PET food packaging, commonly known as plastic wrap in an effort to determine the feasibility of an ellipsometry based measurement system for NS3’s purpose.

Due to its extensive use in the semiconductor industry for monitoring films deposited on silicon, a measurement systems known as ellipsometry, adept at monitoring the thickness and refractive index of thin films deposited on various substrates, appeared to be an ideal system for the measurement of ceramic oxides deposited on various polymer substrates. This project set out to determine the feasibility of using an ellipsometry based measurement system to monitor ceramic films, specifically silicon oxides (SiOX), deposited on polymer products.

A preliminary experiment determined linearly polarized light could induce a discernible change in polarized light traversing a coated beverage container relative to an uncoated container. However, the experiment lacked repeatability due to the measurement apparatus’ cheap setup, prompting the construction of a null (conventional) ellipsometer for further research. The curved surface of the beverage containers under study unnecessarily complicated the feasibility study so further research examined PECVD SiOX on biaxially oriented PET instead.

Characterization of the PECVD SiOX-PET material was divided into three experiments, with the first two analyzing the SiOX film and PET substrate separately while the third analyzed them together. To assist with the characterization experiments, NS3 provided samples, both SiOX coated and uncoated, of various deposition thicknesses on silicon and biaxially oriented PET substrates.

Null ellipsometry was used in conjunction with spectroscopic reflectometry to characterize the refractive index and thickness of the deposited films. The combined measurement systems found the refractive index of the deposited SiOX films to be between 1.461 and 1.465. The measured thicknesses resulting from the two measurement systems coincided well and were usually 10-20 nm thicker than the predicted thicknesses by the deposition processing parameters. Abeles’ method and monochromatic goniometry were attempted; however, the results had to be discarded due to irrecoverable errors discovered in the reflectance measurement. X-ray photoelectron spectroscopy (XPS) data provided by NS3 showed the deposited SiOX films to be homogeneous with stoichiometries between 2.15 and 2.23.

Characterization of the uncoated biaxially oriented PET required numerous measurement systems. From spectroscopic transmission, trirefringent anisotropy was discovered, intertwined with thickness variations in the PET foil. Goniometry measurements displayed distinct interference curves resulting from rear interface reflections interfering with front interface reflections from the PET sample. Subsequent goniometric models produced multiple solutions due to an unknown optical phenomenon, probably scattering, which degraded the reflection measurements. However, a combined measurement technique utilizing goniometry and differential scanning calorimetry (DSC) determined the refractive indices of the polymer to be NX = 1.677, NY = 1.632 and NZ = 1.495 with a thickness of 11.343 μm and a volume fraction crystallinity of 35-41%. Utilizing the measured refractive indices, ellipsometric models produced only an adequate fit of the measured data due to the presence of depolarization caused by non-uniform PET thickness and scattering resulting from embedded microscopic crystallites. The majority of the error in the ellipsometric data was observed in the Δ measurement.

XPS measurements of SiOX deposited on polypropylene (PP) provided by NS3 showed a heterogeneous interphase layer between the deposited oxide and the polymer substrate where the composition of the layer was continually changing. A similar region, which violates the homogenous assumption the ellipsometric model relied on, was anticipated for the SiOX-PET samples under investigation. The use of an effective medium approximation (EMA) to represent the interphase region was attempted, but failed to provide a decent model fit of the measured data. Depolarization and high optical anisotropy caused by the polymer substrate in combination with a heterogeneous interphase region and the effects of the deposited SiOX layer all interacted to prevent ellipsometric modelling of the null ellipsometry measurements conducted. Goniometry measurements were conducted on the thickest deposited SiOX film (approximately 100 nm) which allowed for the refractive index of the film to be approximated through Abeles’ method (n = 1.46); however the validity of this approximation was questionable given the presence of interference fringes resulting from interference between reflections at both the front and rear interfaces of the material.

From the experiments conducted, it was concluded that null ellipsometry with conventional ellipsometric models could not adequately measure a SiOX film’s refractive index or thickness when deposited on biaxially oriented PET. The reasons for the failure were interactions between multiple sources of error which led to both measurement errors and inaccurate model assumptions. Use of generalized ellipsometry, possibly with spectroscopic ellipsometry, may overcome the failures of conventional ellipsometry when studying this complex optical material.

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