Degree Type


Date of Award


Degree Name

Doctor of Philosophy




Analytical Chemistry

First Advisor

Emily A. Smith


Non-destructive optical-based spectroscopic methods are needed for analyzing “real world” devices that consist of thin polymer waveguide films. Many applications (e.g., sensors, microelectronics, optics, and biomedical applications, etc.) utilize thin polymer waveguide films, and non-destructive characterization methods based on Fourier transform (FT)-plasmon waveguide spectroscopy (PWR) and scanning angle (SA) Raman spectroscopy are used to extract optical, physical, and chemical properties simultaneously.

The FT-PWR method measures reflected light at polymer waveguide interface as both the incident frequency (wavelength) and incident angle are scanned. This method uses p- and s-polarized light to simultaneously extract the polymer waveguide thickness and apparent anisotropic indices of refraction. Polystyrene waveguide films ranging from 360 to 800 nm are used to demonstrate the method and it has an average 0.4% relative error when compared to profilometry and atomic force microscopy measurements.

SA Raman spectroscopy is used to measure mixed waveguide polymer films consisting of polystyrene-block-poly(methyl methacrylate) and homopolymer poly(methyl methacrylate) (PS-b-PMMA:PMMA), and poly(2-vinylnapthalene)-block-poly(methyl methacrylate) (P2VN-b-PMMA). PMMA homopolymer is added to the PS-b-PMMA solutions to vary the chemical composition. The chemical composition of each mixed film is quantified (SA Raman peak amplitude ratios) and averaged over all incident angles and is termed the Raman amplitude ratio (rps). This parameter is used to calculate the refractive index of each mixed waveguide polymer film. The refractive index is an input parameter for sum square electric field (SSEF) calculations, which are used to model SA Raman spectra as a function of incident angle to extract the film thickness. The mixed polymer waveguide film thicknesses ranged from 495 to 971 nm, and the SA Raman spectroscopy method has an average 5% difference between the values determined by profilometry.

The SA Raman spectroscopy method developed for mixed polymer waveguide films is used to measure the chemical composition and extract interface locations in bilayer and trilayer films consisting of PMMA/PS or PMMA/PS/PMMA, respectively. The rps value is averaged over angle ranges corresponding to waveguide mode 0 and waveguide mode 1 for the bilayer and trilayer films, respectively. Six multilayer films are analyzed and their total thicknesses range from 330 to 1260 nm. Iterative SSEF calculations are used to model the SA Raman spectra as a function of incident angle, and the best fit to the experimental data is used to extract the total thickness and interface location(s). The method has an axial spatial resolution of 7 to 80 nm and provides comparable values to films measured by profilometry with an average 8% and 7% difference for the bilayer and trilayer films, respectively.


Copyright Owner

Jonathan M. Bobbitt



File Format


File Size

199 pages