This thesis explores the feasibility of high power impulse magnetron sputtering (HiPIMS) to synthesize hydrogenated amorphous carbon (a-C:H) thin films in Ar-hydrocarbon ambient and the relationship between process parameters, gas phase composition and film properties. To this purpose a stable process based on HiPIMS and direct current magnetron sputtering (DCMS) has been developed. Four series of amorphous carbon thin films were deposited by hybrid HiPIMS-DCMS and pure DCMS processes at 15 mTorr pressure using different Ar-acetylene compositions and a substrate bias from 0 to -350 V. The effect of Ar-acetylene compositions and depositions processes on the film properties was investigated by characterizing the films using scanning electron microscopy (SEM), x-ray reflectometry (XRR), nanoindentation and elastic recoil detection analysis (ERDA). Moreover the process characterization was done by recording the optical emission spectrum and current and voltage waveforms of the hybrid HiPIMS-DCMS discharge. The characterization of the films revealed that the hybrid HiPIMS-DCMS process is a powerful tool for controlling the amorphous carbon film properties such as density, deposition rate, hardness and hydrogen content.

The purpose of this study was to examine the psychometric properties of the Precalculus Concept Assessment (PCA), a 25-item multiple-choice instrument designed to assess student reasoning abilities and understanding of foundational calculus concepts (Carlson et al., 2010). When this study was conducted, the extant research on the PCA and the PCA Taxonomy lacked in-depth investigations of the instruments' psychometric properties. Most notably was the lack of studies into the validity of the internal structure of PCA response data implied by the PCA Taxonomy. This study specifically investigated the psychometric properties of the three reasoning constructs found in the PCA taxonomy, namely, Process View of Function (R1), Covariational Reasoning (R2), and Computational Abilities (R3). Confirmatory Factor Analysis (CFA) was conducted using a total of 3,018 pretest administrations of the PCA. These data were collected in select College Algebra and Precalculus sections at a large private university in the mountain west and one public university in the Phoenix metropolitan area. Results showed that the three hypothesized reasoning factors were highly correlated. Rival statistical models were evaluated to explain the relationship between the three reasoning constructs. The bifactor model was the best fitting model and successfully partitioned the variance between a general reasoning ability factor and two specific reasoning ability factors. The general factor was the dominant factor accounting for 76% of the variance and accounted for 91% of the reliability. The omegaHS values were low, indicating that this model does not serve as a reliable measure of the two specific factors. PCA response data were retrofitted to diagnostic classification models (DCMs) to evaluate the extent to which individual mastery profiles could be generated to classify individuals as masters or non-masters of the three reasoning constructs. The retrofitting of PCA data to DCMs were unsuccessful. High attribute correlations and other model deficiencies limit the confidence in which these particular models could estimate student mastery. The results of this study have several key implications for future researchers and practitioners using the PCA. Researchers interested in using PCA scores in predictive models should use the General Reasoning Ability factor from the respecified bifactor model or the single-factor model in conjunction with structural equation modeling techniques. Practitioners using the PCA should avoid using PCA subscores for reasoning abilities and continue to follow the recommended practice of reporting a simple sum score (i.e., unit-weighted composite score).

My dissertation primarily focuses on the fabrication of materials for solid phase microextraction (SPME) and separation devices. In my first project, I used direct current magnetron sputtering (DCMS) to prepare sputtered silicon coatings on fused silica fibers. These fibers were then subjected to the chemical vapor deposition of 6-phenyhexylsilane (6-PH) as a stationary phase. Six different types of fibers were made using two different throw distances (4 cm and 20 cm) and three different silicon thicknesses (0.5, 1.8, and 2.8 µm). These coatings were characterized by time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), spectroscopic ellipsometry (SE), and contact angle goniometry. These SPME fibers were evaluated using gas chromatography (GC). The extraction efficiencies of sputtered, 6-PH-coated fibers were compared to that of a commercial fiber (7 µm PDMS) for polycyclic aromatic hydrocarbons (PAHs). Our 2.8 µm thick sputtered silicon coatings showed competitive extraction of low molecular weight PAHs and ca. 3 times the extraction efficiency for higher molecular weight PAHs. In addition, it outperformed the commercial fiber by showing better linearity, repeatability, and detection limits. A method for analyzing polyaromatic hydrocarbons in baby formula was developed, which showed very good linearity (0.5-125 ppb), repeatability (2-26%), detection limits (0.12-0.81 ppb), and recoveries (103-135%). In my second project, I focused on preparing sputtered carbon SPME fibers using DCMS sputtering. These fibers were tested with and without PDMS coatings on top by SPME-GC-MS. In addition, a new SPME evaluation mix was developed for testing the newly developed SPME fibers. The evaluation mix included analytes with diverse functionalities and properties. Our best carbon fiber showed very competitive extraction capabilities on a per volume basis when compared with a commercial 95 µm carbon-based fiber. In a third project, I built an ALD system to deposit thin films inside GC capillary columns. This system has a unique design that also allows for ALD on witness silicon samples before and after the capillary column. This system yields very promising results with ALD of alumina inside 5 and 12 m long capillary columns. The ALD coatings deposited inside the columns were characterized by transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX). The thicknesses of the coatings on witness shards were almost identical to the thicknesses of the coatings in the capillaries. My fourth project focused on characterizing a liquid polymer (diphenyl siloxane dimethyl siloxane (DPS-DMS)) via SE. This material was a potential stationary phase for our SPME fibers. Transmission measurements were obtained via a dual cuvette approach that eliminated the effects of the cuvettes and their interfaces. The optical function of this material was modeled with a Sellmeier function in its transparent region.

My dissertation focuses on (i) the development sputtered films for solid phase microextraction (SPME) and (ii) the comprehensive characterization of materials using a suite of analytical techniques. Chapter 1 reviews the basics of SPME. This chapter also contains (i) a discussion of various sputtering techniques, (ii) a discussion of two techniques I focused on most of my work: spectroscopic ellipsometry (SE) and X-ray photoelectron spectroscopy (XPS). Chapter 2 focuses the major part of my work, which is to prepare new solid phases/adsorbents for SPME via silicon sputtering followed by thermal deposition of a polymer, polydimethylsiloxane (PDMS). PDMS was deposited by a simple gas phase technique which has never before been applied to prepare SPME stationary phases. The coatings were characterized by time-of-flight mass spectrometry (ToF-SIMS), XPS, scanning electron microscopy (SEM), SE, and contact angle goniometry. The extraction efficiencies of ca. 1.8 µm sputtered, PDMS-coated fibers were compared to a commercial fiber (7 µm PDMS) for a series of polycyclic hydrocarbons (PAHs). Large carry-over and phase bleed peaks are observed in case of commercial PDMS-based SPME coatings, which decrease the lifetime and usefulness of these fibers. It is of great significance that our sputtered fibers exhibit very small or negligible carry-over peaks and phase bleed peaks under the same conditions. Chapter 3 focuses on the multi-instrument characterization of copper and tungsten films sputtered by direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS) using a modern sputter source. The resulting films were characterized by energy dispersive X-ray spectroscopy (EDX), XPS, SEM, atomic force microscopy (AFM), SE, and X-ray diffraction (XRD). By EDX and XPS, all the sputtered films only showed the expected metal peaks. By XPS, the surfaces sputtered by DCMS were richer in oxygen than those produced by HiPIMS. By AFM, both surfaces were quite smooth. By SEM, the HiPIMS films exhibited smaller grain sizes, which was further confirmed by XRD. The crystallite sizes estimated by XRD are as follows: 18.2 nm (W, HiPIMS), 27.3 nm (W, DCMS), 40.2 nm (Cu, HiPIMS), and 58.9 nm (Cu, DCMS). By SE, the HiPIMS surfaces showed higher refractive indices, which suggested that they were denser and less oxidized than the DCMS surfaces. Chapter 4 reports characterization of liquid PDMS via SE, which required some experimental adaptations. The transmission measurements were obtained via a dual cuvette approach that eliminated the effects of the cuvettes and their interfaces. Only the reflection measurements were modeled with a Sellmeier function which produced decent fits. Chapters 5 consists of contributions to Surface Science Spectra (SSS) of near-ambient XPS spectra of various unconventional materials including cheese, kidney stone, sesame seeds, clamshell, and calcite. This dissertation also contains appendices of tutorial articles I wrote on ellipsometry and vacuum equipment.

My dissertation is primarily divided into two parts. The first deals with the preparation, functionalization, and characterization of carbon surfaces prepared by direct current magnetron sputtering (DCMS) and high power impulse magnetron sputtering (HiPIMS) as substrates for bioarrays. Part two discusses applications of XPS peak fitting in surface chemical analysis. Chapter 1, the introduction, includes (i) a discussion of the construction of bioarrays and the preparation of sputtered surfaces, e.g., by DCMS and HiPIMS, and also functionalization (bioconjugate) chemistry with special emphasis on the importance of covalent functionalization of surfaces, and (ii) a discussion of the surface characterization techniques and accompanying analysis methods I have primarily used, which include X-ray photoelectron spectroscopy (XPS), near-ambient pressure XPS (NAP-XPS), XPS peak fitting, and contact angle goniometry (wetting). Chapter 2 discusses the preparation, characterization, and functionalization of DCMS and HiPIMS carbon surfaces for bioarrays. Here, two functionalization chemistries are explored, where the activity of DCMS and HiPIMS carbon towards amidation and amination is compared. Chapter 3 focuses on the use of Gaussian-Lorentzian sum (GLS) and Gaussian-Lorentzian product (GLP) line shapes in the context of peak fitting XPS narrow scans. This discussion includes a comparison of the GLS and GLP line shapes with the Voigt function. Chapters 4 and 5 discuss the applications of XPS peak fitting in materials characterization. Chapter 4 talks about XPS data analysis in the context of the chemical vapor deposition of various aminosilanes and their effect on peptide stability and purity. Chapters 5 describes the surface chemical analysis of various materials by NAP-XPS, including accompanying data analysis and/or peak fitting. The materials probed here cannot be analyzed at ultra-high vacuum by conventional XPS, hence, they are analyzed by NAP-XPS. Chapter 5 is divided into 5 sections. Section 5.1.1 discusses the characterization and analysis of a solution of bovine serum albumin (BSA) by peak fitting the C 1s and O 1s peak envelopes. Section 5.1.2 discusses the analysis of polytetrafluoroethylene (PTFE) at different pressures. Here, the effect of increasing background pressure and X-ray illumination time on the equivalent widths of the F 1s narrows scans is shown. Environmental charge compensation is also discussed here. Section 5.1.3 includes the analysis of poly(γ-benzyl L-glutamate) (PBLG), where the C 1s and O 1s peak envelopes were peak fitted to determine/confirm the structure and composition of this polymer. Section 5.1.4 contains an analysis and comparison of three different human hair samples: (i) untreated, (ii) colored, and (iii) bleached. Here, a comparison of the Si 2p, S 2p, and C 1s peaks illustrates the effects of the different treatments. Section 5.1.5 shows the characterization and analysis of liquid and solid phosphate buffered saline (PBS). Chapter 6 presents conclusion of my work and discusses future work.