The work described herein focuses on FT-IR and quantum cascade laser (QCL) based studies towards the development of compact and portable trace gas sensor for benzene, toluene, and xylenes (BTX). FT-IR broadband radiation was used to probe the mid-infrared fingerprint region for quantitatively detecting trace gas levels of BTX. Using direct absorption through a hollow waveguide, parts-per-million (ppm) detection limits for BTX with a response time of 39 seconds was demonstrated. Univariate calibration provided limits of detection (3σ) for benzene, toluene, and meta-xylene at 5, 17, and 11 ppm, respectively. Multivariate calibration using partial least squares regression algorithms were used to simulate real-world conditions with multiple analytes present within a complex sample. A calibration model was built with 110 training set standards enabled by using a customized gas mixing system. Furthermore, a preconcentration/thermal desorption (TD) step was added to the FT-IR HWG trace gas sensor enabling parts-per-billion detection of BTX. A univariate calibration was established in the laboratory with certified gas standards over a dynamic range of 1000 - 100 ppb for benzene, toluene, and the xylenes. The sensor was then taken to an industrial site during a field measurement campaign for the quantitative determination of BTX in field air samples. The laboratory calibration was used to predict unknown concentrations which were in close agreement with industrial hygiene standard techniques, and industrial prototype analyzers, that were simultaneously operated in the field environment. In addition to FT-IR, quantum cascade laser spectroscopy was also investigated due to enhanced spectral density and efforts to precisely overlap emission with analyte absorption. Particular efforts were dedicated on a novel principle for consistent and deliberate QCL emission wavelength selection by varying the QCL cavity length. These studies experimentally confirmed that using this straight-forward post-processing technique, emission wavelength tuning across a range of one hundred wavenumbers range may be achieved. This tuning range was experimentally demonstrated for a QCL emitting across an entire absorption feature of carbon dioxide by tailoring the length of the cavity. Additionally, using an external cavity (EC) - QCL combined with a HWG gas sensor module for the first time enabled the quantitative and simultaneous determination of ethyl chloride, trichloromethane, and dichloromethane within exponential dilution experiments at ppb limits of detection. Multianalyte detection was demonstrated utilizing partial least squares regression for quantitative discrimination of individual constituents within a mixture, yet applying a single broadly tunable QCL light source.

This thesis presents the integration of atomic vapor cells with anti-resonant reflecting optical waveguides (ARROWs) fabricated on silicon chips. These potentially provide a compact platform for a number of optical applications, including the study of quantum coherence effects such as electromagnetically induced transparency and single-photon nonlinearities, as well as frequency stabilization standards. The use of hollow waveguides allows for light propagation in low index (vapor) media with compact mode areas. ARROWs make particularly attractive waveguides for this purpose because they can be interfaced with solid core waveguides, microfabricated on a planar substrate, and are effectively single mode. ARROW fabrication utilizes an acid-removed sacrificial core surrounded by alternating plasma deposited dielectric layers, which act as Fabry-Perot reflectors. To demonstrate the effectiveness of the ARROW as a vapor cell, a platform consisting of solid and hollow core waveguides integrated with rubidium vapor cells was developed. A variety of sealing techniques were tested for vapor cell integration with the ARROW chip and for compatibility with rubidium. Rubidium was used because it is of particular interest for studying quantum coherence effects. Liquefied rubidium was transferred from a bulk supply into an on-chip vapor cell in an anaerobic atmosphere glovebox. Optical absorption measurements confirmed the presence of rubidium vapor within the hollow waveguide platform. Further analysis of the measurements revealed high optical density of rubidium atoms in the hollow core. Saturated absorption spectroscopy measurements verified that the on-chip integrated vapor cell was suitable for common precision spectroscopy applications.

This dissertation presents a method for fabricating integrated hollow and solid optical waveguides on planar substrates. These waveguides are antiresonant reflecting optical waveguides (ARROWs), where high-index cladding layers confine light to hollow cores through optical interference. Hollow waveguides that can be filled with liquids or gases are an important new building block for creating highly-integrated optical sensors. The method developed for fabricating these integrated waveguides employs standard processes and materials used in the microelectronics industry, allowing for parallel, low-cost fabrication. Dielectric cladding layers are deposited on a silicon wafer using plasma-enhanced chemical vapor deposition (PECVD). After the lower cladding layers have been deposited, a sacrificial material is deposited and patterned using photolithography to produce the hollow-core shape. After the sacrificial cores are defined, they are coated with additional PECVD dielectric layers to form the sides and tops of the waveguides. Integrated solid-core waveguides can be easily created by etching a ridge into the top dielectric cladding layer. Finally, the ends of the sacrificial cores are exposed and removed with an acid solution, resulting in hollow waveguides. Improved optical performance for integrated ARROW platforms can be achieved by only using a single over-coating for the cladding on the sides and top of the hollow waveguide. Such a structure resulted in 70% improvement in optical throughput for the platforms and increased sensitivity for optical manipulation and fluorescence detection of single particles, including viruses. Reduced loss for the hollow waveguides can be obtained by surrounding the core with a terminal layer of air on the sides and top of the waveguide. Such devices were created by forming the hollow waveguides on top of a pedestal on the silicon substrate. This process produces the ideal geometry for hollow ARROW waveguides, and loss measurements of waveguides with air-filled cores had loss coefficients of 1.54/cm, which is the lowest achieved for air-core ARROWs.

This dissertation presents research on the fabrication of optofluidic sensor platforms, which consist of integrated hollow waveguides and solid waveguides. Antiresonant reflecting optical waveguides (ARROWs) filled with liquids or gases, can be used for high-sensitivity sensing in applications of biotechnology, chemical synthesis, and analytical chemistry. The fabrication method developed for integrated ARROW sensing platforms utilizes standard microfabrication processes and materials. Dielectric cladding layers are deposited on a silicon wafer using plasma-enhanced chemical vapor deposition (PECVD) or sputtering. A sacrificial material is then patterned over the bottom cladding layers by photolithography. Additional dielectric layers are deposited around the core, forming the structure of the waveguides. Integrated solid-core waveguides can be easily created by etching a ridge into the topmost dielectric cladding layer. The hollow core waveguides are then formed by wet etching the sacrificial core material. The coupling efficiency between solid core and hollow core waveguides is extremely important for the platform's overall sensitivity. Efficiencies can be enhanced from 18% to 67% by adjusting the thickness of the thick top oxide. Experimental results prove that optical throughput was improved by 17.1× with this improved interface transmission. Sputtered films were investigated as an alternative to for producing cladding layers. The experimental results reveal that sputtered layers show poor adhesion and mechanical strength which make them unreliable for hollow waveguides with small dimension. High-sensitivity ARROW platforms were obtained by employing hybrid layers (PECVD SiO2 and sputtered Ta2O5) as claddings and building waveguides on self-aligned pedestals. The photolumiscence background was only 1/10 that of previous devices made with SiO2/SiN and the average signal-to-noise ratio was improved by 12×.

The mid-infrared (MIR) spectral range (2-20 m) is particularly useful for chemical sensing due to the excitation of fundamental rotational and vibrational modes. In the fingerprint region (10-20 m), most organic analytes have unique absorption patterns; absorption measurements in this region provide molecule-specific information with high sensitivity. Quantum cascade lasers (QCLs) present an ideal light source for (MIR) chemical sensing due to their narrow linewidth, high spectral density, compact size, and ease of fabrication of nearly any MIR wavelength. As the emission wavelength is dependent on layer size within the heterostructure rather than material composition, various wavelengths in the MIR can be achieved through bandstructure engineering. High sensitivity measurements have been achieved in both gas and liquid phase by developing integrated sensing systems. The laser emission frequency is selected to match a strong absorption feature for the analyte of interest where no other interfering bands are located. A waveguide is then developed to fit the application and wavelength used. Gas sensing applications incorporate silica hollow waveguides (HWG) and an OmniGuide fiber (or photonic bandgap HWG). Analyte gas is injected into the hollow core allowing the HWG or OmniGuide to serve simultaneously as a waveguide and miniaturized gas cell. Sensitivities of parts per billion are achieved with a response time of 8 s and a sample volume of approximately 1 mL. Liquid sensing is achieved via evanescent wave measurements with planar waveguides of silver halide (AgX) and gallium arsenide (GaAs). GaAs waveguides developed in this work have a thickness on the order of the wavelength of light achieving single-mode waveguides, providing a significant improvement in evanescent field strength over conventional multimode fibers. Liquid samples of L volume at the waveguide surfaces are detected. QCLs have begun to be utilized as a light source in the MIR regime over the last decade. The next step in this field is the development of compact and highly integrated device platforms which take full advantage of this technology. The sensing demonstrations in this work advance the field towards finding key applications in medical, biological, environmental, and atmospheric measurements.

As the microelectronics industry pushes microfabrication processes further, the lab-on-a-chip field has continued to piggy-back off the industry's fabrication capabilities with the goal of producing total chemical and biological systems on small chip-size platforms. One important function of such systems is the ability to perform single molecule detection. There are currently many methods being researched for performing single molecule detection, both macro and micro in scale. This dissertation focuses on an optofluidic, lab-on-a-chip platform called the ARROW biosensor, which possesses several advantages over macro-scale single molecule detection platforms. These advantages include an amplification-free detection scheme, cheap parallel fabrication techniques, rapid single molecule detection results, and extremely low volume sample probing, which leads to ultra-sensitive detection. The ARROW biosensor was conceived in the early 2000s; however, since then it has undergone many design changes to improve and add new functionality to the lab-on-a-chip; however, water absorption in the plasma enhanced chemical vapor deposited silicon dioxide has been a problem that has plagued the biosensor platform for some time. Moisture uptake in the oxide layer of the ARROWs leads to loss of waveguiding confinement and drastically decreases the overall sensitivity of the ARROW biosensors. New ARROW designs were investigated to alleviate the negative water absorption effects in the ARROWs. The new waveguide designs were tested for resiliency to water absorption and the buried ARROW (bARROW) design was determined to be the most successful at preventing negative water absorption effects from occurring in the PECVD oxide waveguides. The bARROWs were integrated into the full biosensor platforms and used to demonstrate high sensitivity single molecule detection without any signs of water absorption affecting the bARROWs' waveguiding capabilities. The bARROW biosensors are not only water resistant, they also proved to be the most sensitive biosensors yet fabricated with average signal-to-noise ratios around 80% higher than any previously fabricated ARROW biosensors.

Optofluidics is a relatively new and exciting field that includes the integration of optical waveguides into microfluidic platforms. The purpose of this field of study is to miniaturize previously developed optical systems used for biological and chemical analysis with the end goal of placing bench-top optics into microscopic packages. Mundane optical alignment and sample manipulation procedures would then be intrinsic to the platform and allow measurements to be completed quickly and with reduced human interaction. Biosensors based on AntiResonant Reflecting Optical Waveguides (ARROWs) consist of hollow-core waveguides used for fluid sample manipulation and analysis, as well as solid-core waveguides used in interfacing external components located at the chip edges. Hollow-core ARROWs are particularly useful for their ability to provide specifically tailored analyte volumes that are easily configurable depending upon the target experiment. Adaptations of standard planar microfabrication methods allow for complex integrated ARROW designs. Integrated spectral filtering with high rejection can be implemented on-chip, removing the need for additional off-chip components and increasing device sensitivity. Additional techniques to increase device sensitivity and utility, such as hybrid ARROW platforms and optical manipulation of samples, are also explored.

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